Liquid composition, device, method of manufacturing porous resin, porous resin, product, and method of manufacturing porous resin

ABSTRACT

A liquid composition that contains a polymerizable compound and a solvent, and that can form a porous resin. The liquid composition, when stirred, transmits at least 30 percent of incident light having a wavelength of 550 nm. The haze value of an containing the liquid composition increases by 1.0 percent or more when the element containing the liquid composition is cured.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application is a divisional of U.S. patent application Ser.No. 16/727,443, which is based on and claims priority pursuant to 35U.S.C. § 119 to Japanese Patent Application Nos. 2018-242225,2019-198476, and 2019-212264, filed on Dec. 26, 2018, Oct. 31, 2019, andNov. 25, 2019, respectively, in the Japan Patent Office, the entiredisclosures of which are hereby incorporated by reference herein.

BACKGROUND Technical Field

The present invention relates to a liquid composition, a device, amethod of manufacturing a porous resin, a porous resin, a productcontaining the porous resin, and a method of manufacturing a porousresin.

Description of the Related Art

Porous media and porous membranes can be utilized in a variety ofapplications, including separation membranes, adsorbing membranes, andlead battery separators, based on their unique functions. Therefore, theapplication will be wider if there is a porous forming liquidcomposition that is easy to handle and is easily applicable to variousplaces.

As a method of forming a porous medium, a method of forming a porousmedium by laminating fine particles has been proposed. This methodrequires a solution in which fine particles are dispersed, but it isdifficult to stably maintain the dispersion state of the solutioncontaining the fine particles. Further, when a porous medium is formedby plate printing, fine particles wears the application device, whichleads to deterioration of product quality over a long time.

SUMMARY

According to embodiments of the present disclosure, provided is a liquidcomposition that contains a polymerizable compound and a solvent, andthat can form a porous resin. The liquid composition, when stirred,transmits at least 30 percent of incident light having a wavelength of550 nm. The haze value of an containing the liquid composition increasesby 1.0 percent or more when the element containing the liquidcomposition is cured.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

Various other objects, features and attendant advantages of the presentinvention will be more fully appreciated as the same becomes betterunderstood from the detailed description when considered in connectionwith the accompanying drawings in which like reference charactersdesignate like corresponding parts throughout and wherein:

FIG. 1 is a schematic diagram illustrating an example of a device formanufacturing a porous resin that executes a method of manufacturing theporous resin according to an embodiment of the present disclosure; and

FIG. 2 is a schematic diagram illustrating an example of a fabricationdevice employing a material jet method.

The accompanying drawings are intended to depict example embodiments ofthe present invention and should not be interpreted to limit the scopethereof. The accompanying drawings are not to be considered as drawn toscale unless explicitly noted. Also, identical or similar referencenumerals designate identical or similar components throughout theseveral views.

DESCRIPTION OF THE EMBODIMENTS

In describing embodiments illustrated in the drawings, specificterminology is employed for the sake of clarity. However, the disclosureof this specification is not intended to be limited to the specificterminology so selected and it is to be understood that each specificelement includes all technical equivalents that have a similar function,operate in a similar manner, and achieve a similar result.

As used herein, the singular forms “a”, “an”, and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise.

Moreover, image forming, recording, printing, modeling, etc., in thepresent disclosure represent the same meaning, unless otherwisespecified.

Embodiments of the present invention are described in detail below withreference to accompanying drawing(s). In describing embodimentsillustrated in the drawing(s), specific terminology is employed for thesake of clarity. However, the disclosure of this patent specification isnot intended to be limited to the specific terminology so selected, andit is to be understood that each specific element includes all technicalequivalents that have a similar function, operate in a similar manner,and achieve a similar result.

For the sake of simplicity, the same reference number will be given toidentical constituent elements such as parts and materials having thesame functions and redundant descriptions thereof omitted unlessotherwise stated.

A porous-forming photocurable resin composition has been proposed in JP2004-51783-A1 which contains a photopolymerizable monomer A, an organiccompound B incompatible with the photopolymerizable monomer A, a commonsolvent C compatible with both the photopolymerizable monomer A and theorganic compound B, and a photopolymerization initiator D as requisites.

However, in JP 2004-51783-A1 mentioned above, since it is necessary tomix at least two types of solvents having a specific relationship, itlimits the selection of usable materials, thereby making the materialdesigning difficult. Moreover, in order to be a liquid composition forforming a porous resin that can be applicable to various applicationmethods, high compatibility is required between the polymerizablecompound and the solvent contained in the liquid composition.

According to the present disclosure, an easily designable liquidcomposition containing a polymerizable compound and a solvent highlycompatible with each other is obtained for forming a porous resin.

Next, an embodiment of the present disclosure is described.

The liquid composition of this embodiment contains a polymerizablecompound and a solvent and can form a porous resin, wherein the liquidcomposition, when stirred, transmits at least 30 percent of incidentlight having a wavelength of 550 nm and wherein, when an elementcomprising the liquid composition is cured, the haze value of theelement increases by 1.0 percent or more.

Liquid Composition

The liquid composition of this embodiment contains a polymerizablecompound, a solvent, and other optional components such as apolymerization initiator. The liquid composition can form a porous resinby curing, etc. For this reason, the liquid composition is preferablyused as a liquid for forming a porous resin.

In the present embodiment, “the liquid composition forms a porous resin”not only means that the porous resin is formed in the liquid compositionbut also a porous resin precursor in the liquid composition is formedand is subject to a subsequent process such as heating process to formthe porous resin. Moreover, it also includes not only when the entireliquid composition cures to form a porous resin but also when a part ofthe liquid composition, which is the polymerizable compound, etc., iscaused to cure (i.e., polymerize) to form a porous resin and the rest ofthe liquid composition, which is the solvent, etc., does not form aporous resin.

Polymerizable Compound

Polymerizable compounds are polymerized to form a resin and furtherforms a porous resin when polymerized in the liquid composition. Theresin formed of the polymerizable compound preferably has a networkstructure formed upon an application of active energy rays (for example,irradiation of light or application of heat). Preferable examplesinclude, but are not limited to, acrylate resins, methacrylate resins,urethane acrylate resins, vinyl ester resins, unsaturated polyesterresins, epoxy resins, oxetane resins, vinyl ether resins, and resinsformed by an ene-thiol reaction. In addition, acrylate resins,methacrylate resins, and urethane acrylate resins, which are formed of apolymerizable compound having a (meth)acryloyl group, vinyl esterresins, which are formed by a polymerizable compound having a vinylgroup are more preferable in terms of easiness of forming a structureusing radical polymerization with high reactivity and productivity andproductivity. These can be used alone or in combination. When two ormore types are used in combination, the combination of the polymerizablecompounds is not particularly limited and can be suitably selected tosuit to a particular application. It is preferable to mix a urethaneacrylate resins as the main component with other resins to impartflexibility. In the present disclosure, a polymerizable compound havingan acryloyl group or a methacryloyl group is referred to as apolymerizable compound having a (meth)acryloyl group.

The active energy ray is not particularly limited as long as it canprovide energy to proceed the polymerization reaction of thepolymerizable compound in the liquid composition. For example,ultraviolet rays, electron beams, α rays, β-rays, γ-rays, and X-rays canbe used. Of these, ultraviolet rays are preferable. A particularly highenergy light source obviates the need for a polymerization initiator toproceed polymerization reaction.

The polymerizable compound preferably has at least one radicalpolymerizable functional group. Examples include, but are not limitedto, monofunctional, bifunctional, trifunctional or higher radicalpolymerizable compounds, functional monomers, and radical polymerizableoligomers. Of these, a bifunctional or higher radical polymerizablecompound is preferred.

Specific examples of the monofunctional radical polymerizable compoundinclude, but are not limited to, 2-(2-ethoxyethoxy)ethyl acrylate,methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycolmonomethacrylate, phenoxypolyethylene glycol acrylate,2-acryloyloxyethyl succinate, 2-ethylhexyl acrylate, 2-hydroxyethylacrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate,2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzylacrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate,methoxytriethylene glycol acrylate, phenoxytetraethylene glycolacrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, andstyrene monomers. These can be used alone or in combination.

Specific examples of the bifunctional radical polymerizable compoundinclude, but are not limited to, 1,3-butane diol acrylate, 1,4-butanediol acrylate, 1,4-butane diol dimethacrylate, 1,6-hexane dioldiacrylate, 1,6-hexane diol dimethaacrylate, diethylene glycoldiacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate,bisphenol A EO-modified diacrylate, bisphenol F EO-modified diacrylate,neopentyl glycol diacrylate, and tricyclodecane dimethanol diacrylate.These can be used alone or in combination.

Specific examples of the tri- or higher radical polymerizable compoundinclude, but are not limited to, trimethylol propane triacrylate(TMPTA), trimethylol propane trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylol propane triacrylate,caprolactone-modified trimethylol propane triacrylate, HPA-modifiedtrimethylol propane triacrylate, pentaerythritol triacrylate,pentaerythritol tetra acrylate (PETTA), glycerol triacrylate,ECH-modified glycerol triacrylate, EO-modified glycerol triacrylate,PO-modified glycerol triacrylate, tris(acryloxyrthyl)isocyanulate,dipenta erythritol hexacrylate (DPHA), caprolactone-modified dipentaerythritol hexacrylate, dipenta erythritol hydroxyl dipenta acrylate,alkylized dipenta erythritol tetracrylate, alkylized dipenta erythritoltriacrylate, dimethylol propane tetracrylate (DTMPTA), penta erythritolethoxy tetracrylate, EO-modified phosphoric acid triacrylate, and2,2,5,5-tetrahydroxy methyl cyclopentanone tetracrylate. These can beused alone or in combination.

The proportion of the polymerizable compound in the liquid compositionis preferably from 5.0 to 70.0 percent by mass, more preferably from10.0 to 50.0 percent by mass, and furthermore preferably from 20.0 to40.0 percent by mass. When the proportion of the polymerizable compoundis 70.0 percent by mass or less, the pore size of the obtained porousmedium is a few nm or less, which is not too small, the porous mediumhas an appropriate porosity so that it is possible to reduce thetendency to make it difficult for liquid or air to permeate the porousmedium, which is preferable. In addition, when the proportion of thepolymerizable compound is 5.0 percent by mass or more, athree-dimensional network structure of the resin is sufficiently formedto obtain a sufficient porous structure, and the strength of theobtained porous structure is enhanced. This is preferable.

Solvent

The solvent (hereinafter also referred to as “porogen” in the followingdescription) is compatible with the polymerizable compound. The solventis a liquid that becomes incompatible (meaning causing phase separation)with the polymer (resin) in the process of polymerization of thepolymerizable compound in the liquid composition. When the solvent iscontained in the liquid composition, the polymerizable compound forms aporous resin at the polymerization in the liquid composition. Moreover,it is preferable to dissolve a compound (polymerization initiatordescribed later) that produces a radical or an acid by light or heat.These can be used alone or in combination. In this embodiment, thesolvent is not polymerizable.

The boiling point of the porogen alone or in combination of two or moreis preferably from 50 to 250 degrees C. and more preferably from 70 to200 degrees C. at normal pressure. When the boiling point is 50 degreesC. or higher, vaporization of the porogen around the room temperature isreduced so that, the liquid composition is easily handled and thecontrol of the proportion of the porogen in the liquid compositionbecomes easy. Moreover, when the boiling point is 250 degrees C. orlower, the time taken to dry the porogen after the polymerization isshortened and the productivity of the porous resin is improved. Inaddition, since the proportion of the porogen remaining inside theporous resin can be reduced, the porous resin can be used as afunctional layer such as a substance separation layer for separatingsubstances and a reaction layer as a reaction field, which enhancesquality.

Moreover, it is preferable that the boiling point as one type of porogenor the boiling point when using two or more types together be 120degrees C. or higher at a normal pressure.

Specific examples of the porogen include, but are not limited to,ethylene glycols such as diethylene glycol monomethyl ether, ethyleneglycol monobutyl ether, ethylene glycol monoisopropyl ether, anddipropylene glycol monomethyl ether, esters such as γ-butyrolactone andpropylene carbonate, and an amide such as NN dimethylacetamide. Inaddition, other examples include liquids having a relatively largemolecular weight such as methyl tetradecanoate, methyl decanoate, methylmyristate, and tetradecane. Further, liquids such as acetone,2-Ethylhexanol, and 1-bromonaphthalene can also be mentioned.

In the present embodiment, the liquid specified above is not always aporogen. The porogen in the present embodiment is compatible with thepolymerizable compound as described above and becomes incompatible(i.e., causing phase separation) with the polymer (resin) in the courseof polymerization of the polymerizable compound in the liquidcomposition. In other words, whether a liquid is a porogen depends onthe relationship between a polymerizable compound and the polymer (resinformed by polymerization of the polymerizable compound).

In addition, since the liquid composition of the present embodiment onlyneeds to contain at least one porogen having this specific relationshipwith a polymerizable compound, the latitude of material selection at thetime of preparing the liquid composition is large, which makes thedesign of the liquid composition easy. Due to the high level of latitudeof material selection at the time of preparation of a liquidcomposition, a variety of properties for the liquid composition otherthan the formation of a porous structure can be handled. For example,when a liquid composition is discharged by an inkjet method, the liquidcomposition is required to have discharging stability. However, theliquid composition is easily designed because the material can beselected from a wide range.

In addition, as long as the liquid composition of this embodimentcontains at least one type of porogen having the specific relationshipmentioned above with the polymerizable compound, a liquid not havingthis specific relationship (liquid that is not porogen) may be added.However, the proportion of the liquid not having this specificrelationship (liquid that is not a porogen) with the polymerizablecompound is preferably 10.0 percent by mass or less, 5.0 percent by massor less, and furthermore preferably 1.0 percent by mass or less to thetotal amount of the liquid composition.

The proportion of the porogen in the liquid composition is preferablyfrom 30.0 to 95.0 percent by mass, more preferably from 50.0 to 90.0percent by mass, and furthermore preferably from 60.0 to 80.0 percent bymass. When the proportion of the porogen is 30.0 percent by mass ormore, the pore size of the obtained porous medium is a few nm or less,which is not too small, the porous medium has an appropriate porosity sothat it is possible to reduce the tendency to make it difficult forliquid or air to permeate the porous medium, which is preferable. Inaddition, when the proportion of the porogen is 95.0 percent by mass orless, a three-dimensional network structure of the resin is sufficientlyformed to obtain a sufficient porous structure, and the strength of theobtained porous structure is enhanced, which is preferable.

The mass ratio of the polymerizable compound to the porogen in theliquid composition is preferably from 1.0:0.4 to 1.0:19.0, morepreferably from 1.0:1.0 to 1.0:9.0, and furthermore preferably from1.0:1.5 to 1.0:40.

Polymerization-Induced Phase Separation

In this embodiment, a porous resin is formed by polymerization-inducedphase separation. In the polymerization-induced phase separation in thisembodiment, the polymerizable compound and the porogen are compatible,however, the polymer (resin) produced in the process of polymerizationof the polymerizable compound and the porogen are incompatible with eachother (phase separation occurs). Although there are other methods forobtaining a porous medium by phase separation, a porous medium having anetwork structure can be formed by using the polymerization-inducedphase separation method, so that the obtained porous medium is expectedto have highly chemical resistance and heat resistance. Further, ascompared with other methods, there are also advantages such as a shortprocess time and easy surface modification.

Next, a process for forming a porous resin using polymerization-inducedphase separation will be described. A polymerizable compound causespolymerization reaction by light irradiation, etc., to form a resin.During this process, solubility of the growing resin in the porogendecreases. As a consequence, phase separation occurs between the resinand the porogen. Finally, the resin forms a porous structure having anetwork structure having a porous structure in which the pores arefilled with the porogen, etc. When this is dried, the porogen, etc., areremoved and the porous resin remains. Therefore, in order to form aporous resin having an appropriate porosity, the compatibility betweenthe porogen and the polymerizable compound and the compatibility betweenthe porogen and the resin formed by polymerizing the polymerizablecompound are investigated.

Hansen Solubility Parameter (HSP)

The compatibility described above can be predicted through the Hansensolubility parameter (HSP). The Hansen Solubility Parameter (HSP) is auseful tool for predicting the compatibility of two substances, aparameter discovered by Charles M. Hansen. Hansen Solubility Parameter(HSP) is represented by combining the following experimentally andtheoretically derived three parameters (δD, δP, and δH). Hansensolubility parameter (HSP) is represented in MPa^(0.5) or (J/cm³)^(0.5).In this embodiment (J/cm³)^(0.5) is employed.

-   -   δD: Energy derived from London dispersion force    -   δP: Energy derived from dipole interaction    -   δH: Energy derived from hydrogen bonding force

The Hansen solubility parameter (HSP) is a vector quantity representedas (δD, δP, δH), and represented by plotting on a three-dimensionalspace (Hansen space) having these three parameters as coordinate axes.For the Hansen solubility parameters (HSP) of commonly used substances,there is a known information source such as a database. Therefore, forexample, the Hansen solubility parameter (HSP) of a substance isobtained by referring to the database. Regarding a substance whoseHansen Solubility Parameters (HSP) is not registered in the database, itcan be calculated from the chemical structure of the substance andHansen Solubility Sphere Method described later using computer softwaresuch as Hansen Solubility Parameters in Practice (HSPiP). The Hansensolubility parameter (HSP) of a mixture containing two or moresubstances is calculated as a vector sum of values obtained bymultiplying the Hansen solubility parameter (HSP) of each substance bythe volume ratio of each substance to the entire mixture. In the presentembodiment, the Hansen solubility parameter (HSP) of the solvent(porogen) obtained based on a known information source such as adatabase is referred to as “Hansen solubility parameter of solvent”.

Also, the relative energy difference (RED) based on the Hansensolubility parameter (HSP) of a solute and the Hansen solubilityparameter (HSP) of a solution is represented by the following mathematicexpression.Relative energy difference (RED)=Ra/Ro

In the mathematic expression, Ra represents the HSP distance between theHansen solubility parameter (HSP) of a solute and the Hansen solubilityparameter (HSP) of a solution, and Ro represents the interaction radiusof the solute. The HSP distance (Ra) between the Hansen SolubilityParameters (HSP) indicates the distance between the two substances. Asmaller value means that two types of substances are closer to eachother in the three-dimensional space (Hansen space) and indicates thatthe possibility of mutual dissolution (compatibility) increases.

Assuming that the respective Hansen solubility parameters (HSP) for thetwo substances (solute A and solution B) are as follows, Ra can becalculated as follows:HSP^(A)=(δD ^(A) ,δP ^(A) ,δH ^(A))HSP^(B)=(δD ^(B) ,δP ^(B) ,δH ^(B))Ra=[4×(δD ^(A) −δD ^(B))²+(δP ^(A) −δP ^(B))²+(δH ^(A) −δH ^(B))²]^(1/2)

Ro (interaction radius of solute) can be determined by, for example, theHansen solubility sphere method described below.

Hansen Solubility Sphere Method

First, a substance whose Ro is required and several dozens of solventsfor evaluation having known Hansen solubility parameters (HSP) (liquidswhich are different from the above-mentioned “solvent (porogen)”) areprepared and subjected to a compatibility test of the substance to eachof the solvents for evaluation. In the compatibility test, the Hansensolubility parameter (HSP) of the solvents for evaluation demonstratingcompatibility and the Hansen solubility parameter (HSP) of the solventsfor evaluation not demonstrating compatibility are plotted in the Hansenspace. Based on the Hansen solubility parameter (HSP) of each of theplotted solvents for evaluation, a virtual sphere (Hansen sphere) iscreated including the Hansen solubility parameters (HSP) of the solventgroup for evaluation demonstrating compatibility while excluding theHansen solubility parameters of the solvent group for evaluation notdemonstrating compatibility. The radius of the Hansen sphere is theinteraction radius Ro of the substance and the center is the Hansensolubility parameter (HSP) of the substance. Note that an evaluatorhimself sets the evaluation criteria (whether or not the subject iscompatible) for compatibility between a substance to obtain theinteraction radius Ro and Hansen solubility parameter (HSP) and asolvent for evaluation whose Hansen solubility parameter (HSP) is known.The evaluation criteria in this embodiment will be described later.

Hansen Solubility Parameter (HSP) and Interaction Radius ofPolymerizable Compound

Hansen solubility parameter (HSP) of the polymerizable compound in thisembodiment and the interaction radius of the polymerizable compound aredetermined by the Hansen solubility sphere method. As described above,the evaluation criteria for compatibility in the Hansen solubilitysphere method are set by the evaluator himself. Therefore, the Hansensolubility parameter (HSP) of the polymerizable compound in the presentembodiment obtained by the following criteria is referred to as Hansensolubility parameter C of the polymerizable compound and the interactionradius of the polymerizable compound is represented as interactionradius D of the polymerizable compound. In other words, unlike theHansen solubility parameter (HSP) of the solvent obtained based on aknown data sources such as database, the Hansen solubility parameter Cof the polymerizable compound and the interaction radius D of thepolymerizable compound are obtained based on the Hansen solubilitysphere method including the evaluation criteria of compatibility set bythe evaluator himself.

According to the following [1-1] and [1-2], the Hansen solubilityparameter C of a polymerizable compound and the interaction radius D ofthe polymerizable compound are obtained by the evaluation ofcompatibility between the polymerizable compound and a solvent forevaluation, which is based on light transmission of the composition formeasuring transmission measured at a wavelength of 550 nm while stirringa composition for measuring transmission containing the polymerizablecompound and the solvent for evaluation.

[1-1] Preparation of Composition for Measuring Transmission

First, a polymerizable compound whose Hansen solubility parameter (HSP)is desired and several dozen types of solvents for evaluation with knownHansen solubility parameters (HSP) are prepared and the polymerizablecompound, each solvent for evaluation, and a polymerization initiatorare mixed with the following ratio to prepare the composition formeasuring transmission. Dozens of solvents for evaluation with knownHansen solubility parameters (HSP) are 21 types of solvents forevaluation below.

Ratio of Composition for Measuring Transmission

-   -   Polymerizable compound whose Hansen solubility parameter (HSP)        is desired: 28.0 percent by mass    -   Solvent for evaluation with known Hansen solubility parameter        (HSP): 70.0 percent by mass    -   Polymerization initiator (Irgacure 819, manufactured by BASF        SE): 2.0 percent by mass

Solvent Group (21 types) for Evaluation

Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether,N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethylether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone,n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether,diethylene glycol butyl ether acetate, methyl ethyl ketone, methylisobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, and1-bromonaphthalene

[1-2] Measurement of Light Transmission

The prepared composition for measuring transmission is infused into aquartz cell and the transmission of light (visible light) having awavelength of 550 nm of the composition for measuring transmission ismeasured while stirring at 300 rpm using a stir bar. In this embodiment,when the light transmission is 30 percent or more, the polymerizablecompound and the solvent for evaluation are determined as a compatiblestate. When the light transmission is less than 30 percent, thepolymerizable compound and the solvent for evaluation are determined asincompatible. Various conditions regarding the measurement of lighttransmission are as follows:

-   -   Quartz cell: Special micro cell with screw cap (trade name:        M25-UV-2)    -   Transmission measuring device: USB4000, manufactured by Ocean        Optics, Inc    -   Rate of stirring: 300 rpm    -   Measuring wavelength: 550 nm    -   Reference: Measures light transmission at a wavelength of 550 nm        with the quartz cell filled with air (transmission: 100 percent)

Another example of the present embodiment in which the polymerizablecompound and the solvent (porogen) contained in the liquid composition(distinguished from the above-described composition for measuringtransmission) are compatible is as follows. That is, the lighttransmission is measured using the liquid composition instead of thecomposition for measuring transmission in the [1-2] without executingthe [1-1]. At the time, when the light transmission is 30 percent ormore, it is determined that the polymerizable compound and the solvent(porogen) contained in the liquid composition are compatible. When thelight transmission is less than 30 percent or more, it is determined asincompatible. In the present embodiment, the light transmission measuredusing the liquid composition instead of the composition for measuringtransmission in [1-2] is referred to as the light transmission of theliquid composition measured at a wavelength of 550 nm during stirringthe liquid composition.

Hansen Solubility Parameter (HSP) and Interaction Radius of Resin Formedby Polymerization of Polymerizable Compound

Hansen solubility parameter (HSP) of the resin formed by thepolymerization of the polymerizable compound in the present embodimentand the interaction radius of the resin formed by the polymerization ofthe polymerizable compound are determined by the Hansen solubilitysphere method. As described above, the evaluation criteria forcompatibility in the Hansen solubility sphere method are set by theevaluator himself. Therefore, the Hansen solubility parameter (HSP) ofthe resin formed by the polymerization of the polymerizable compound inthe present embodiment according to the following criteria isrepresented as Hansen solubility parameter A of the resin and theinteraction radius of the resin formed by the polymerization of thepolymerizable compound is represented as the interaction radius B of theresin. In other words, unlike the Hansen solubility parameter (HSP) ofthe solvent obtained based on a known data sources such as database, theHansen solubility parameter A of the resin and the interaction radius Bof the resin are obtained based on the Hansen solubility sphere methodincluding the evaluation criteria of compatibility set by the evaluatorhimself.

The Hansen solubility parameter A of the resin and the interactionradius B of the resin are obtained by evaluating the compatibility ofthe resin with the solvent for evaluation according to the following[2-1], [2-2] and [2-3], which is based on the increasing ratio of haze(cloudiness) value in an element for measuring haze prepared using apolymerizable compound and a composition for measuring haze containing asolvent for evaluation.

[2-1] Preparation of Composition for Measuring Transmission

First, a precursor (polymerizable compound) of a resin whose Hansensolubility parameter (HSP) is desired and several dozen types ofsolvents for evaluation with known Hansen solubility parameters (HSP)are prepared. Thereafter, the polymerizable compound, each solvent forevaluation, and a polymerization initiator are mixed with the followingratio to prepare the composition for measuring haze. Dozens of solventsfor evaluation with known Hansen solubility parameters (HSP) are 21types of solvents for evaluation below.

Ratio of Composition for Measuring Haze

-   -   Precursor (polymerizable compound) of resin whose Hansen        solubility parameter (HSP) is desired: 28.0 percent by mass    -   Solvent for evaluation with known Hansen solubility parameter        (HSP): 70.0 percent by mass    -   Polymerization initiator (Irgacure 819, manufactured by BASF        SE): 2.0 percent by mass

Solvent Group (21 Types) for Evaluation

Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether,N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethylether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone,n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether,diethylene glycol butyl ether acetate, methyl ethyl ketone, methylisobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, and1-bromonaphthalene

[2-2] Preparation of Element for Measuring Haze

Resin particulates are uniformly dispersed on an alkali-free glasssubstrate by spin coating to obtain a gap agent. Subsequently, thesubstrate coated with the gap agent and an alkali-free glass substrateto which no gap agent is applied are attached to each other in such amanner that the gap agent is sandwiched between the substrate and thealkali-free glass substrate. Next, the composition for measuring hazeprepared in [2-1] is filled into between the attached substratesutilizing the capillary phenomenon to produce an element for measuringhaze before UV irradiation. Subsequently, the element for measuring hazebefore UV irradiation is irradiated with UV to cause the composition formeasuring haze to cure. Finally, the periphery of the substrate issealed with a sealant to prepare the element for measuring haze. Variousconditions at the time of preparation are as follows.

-   -   Alkali-free glass substrate: OA-10G, 40 mm, t=0.7 mm,        manufactured by Nippon Electric

Glass Co., Ltd.

-   -   Gap agent: Resin fine particles Micropearl GS-L100, average        particle size 100 manufactured by SEKISUI CHEMICAL CO., LTD.    -   Spin coating conditions: Amount of dispersing droplet 150 μL,        rate of rotation 1,000 rpm, time of rotation 30 s    -   Amount of filled composition for measuring haze: 160 μL    -   UV irradiation conditions: UV-LED is used as a light source,        light source wavelength 365 nm, irradiation intensity 30 mW/cm²,        time of irradiation 20 seconds    -   Sealant: TB3035B (manufactured by ThreeBond Co., Ltd.)

[2-3] Measurement of Haze Value (Cloudiness)

The haze value (cloudiness) is measured using the prepared element formeasuring haze before UV irradiation and the element for measuring haze.Using the measurement value for the element for measuring haze before UVirradiation as a reference (haze value 0), the increasing ratio of themeasurement value (haze value) for the element for measuring haze to themeasurement value (haze value) for the element for measuring haze beforeUV irradiation is calculated. The haze value in the element formeasuring haze increases as the compatibility between the resin formedby polymerization of the polymerizable compound and the solvent forevaluation decreases and the haze value decreases as the compatibilityincreases. Moreover, as the haze value increases, the resin formed bypolymerization of polymerizable compound tends to form a porousstructure. In this embodiment, when the increase ratio of the haze valueis 1.0 percent or more, the resin and the solvent for evaluation aredetermined as incompatible. When the increase ratio is less than 1.0percent, the resin and the solvent for evaluation are determined ascompatible. The instruments used for the measurement are as follows.

-   -   Haze measuring device: Haze meter NDH5000, manufactured by        Nippon Denshoku Industries Co., Ltd.

Another example of the present embodiment in which the polymerizablecompound and the solvent (porogen) contained in the liquid composition(distinguished from the composition for measuring haze mentioned above)are incompatible (phase separation occurs) is as follows. First, in the[2-2] executed without executing the [2-1], the liquid composition isused instead of the composition for measuring haze to prepare an elementfor measuring haze before UV irradiation and an element for measuringhaze. Next, the increase ratio of the haze value is measured using theelement for measuring haze before UV irradiation and the element formeasuring haze using the liquid composition in the [2-3]. At the time,when the increase ratio of the haze value is 1.0 percent or more, thepolymer (resin) and the solvent (porogen) contained in the liquidcomposition are determined as incompatible. I.e., phase separationoccurs. When the increase ratio is less than 1.0 percent, it isdetermined as compatible, i.e., phase separation does not occur. In thepresent embodiment, the element for measuring haze prepared using theliquid composition instead of the composition for measuring haze in the[2-2] is referred to as the element for measuring haze prepared usingthe liquid composition.

Relative Energy Difference (RED) 1 Based on Hansen Solubility Parameter(HSP) of Resin and Solvent (Porogen)

The relative energy difference (RED) 1, based on a Hansen solubilityparameter (HSP) A of a resin formed by polymerizing the polymerizablecompound, an interaction diameter B of the resin, and an HSP of thesolvent, is 1.00 or greater, wherein RED 1={Distance between (the HSP Aof the resin) and (the HSP of the solvent)}/(the interaction diameter Bof the resin) Relationship 1. RED 1 is more preferably 1.10 or greater,furthermore preferably 1.20 or greater, and particularly preferably 1.30or greater.

When RED 1 based on the Hansen solubility parameter (HSP) of the resinand the porogen is 1.00 or greater, the resin formed by polymerizationof the polymerizable compound in the liquid composition and the porogenare likely to cause phase separation and a porous resin is easilyformed, which is preferable.

Relative Energy Difference (RED) 2 Based on Hansen Solubility Parameter(HSP) of Polymerizable Compound and Solvent (Porogen)

As described above, the relative energy difference (RED) 2, based on theHansen solubility parameter (HSP) C of the polymerizable compounddetermined based on the light transmission at a wavelength of 550 nm ofthe composition for measuring transmission measured when stirring thecomposition for measuring transmission containing the polymerizablecompound and the solvent for evaluation, the interaction radius D of thepolymerizable compound determined based on the compatibility of thepolymerizable compound and the solvent for evaluation, and the Hansensolubility parameter of the solvent, is preferably 1.05 or less, morepreferably 0.90 or less, furthermore preferably 0.80 or less, andpreferably 0.70 or less. RED 2={Distance between (the HSP C of thepolymerizable compound) and (the HSP of the solvent)}/(the interactiondiameter D of the polymerizable compound) Relationship 2

When RED 2 based on the Hansen solubility parameter (HSP) of thepolymerizable compound and the porogen is 1.05 or less, thepolymerizable compound and the porogen tend to be compatible. As the RED2 approaches zero, the both become more compatible. For this reason,when the RED 2 is 1.05 or less, a liquid composition is obtained whichdemonstrates a high level of solution stability in which thepolymerizable compound does not precipitate over time after thepolymerizable compound is dissolved in the porogen. Since thepolymerizable compound has a high level of solubility in the porogen,discharging stability of the liquid composition can be maintained. Forexample, the liquid composition of the present embodiment can be appliedto the method of discharging the liquid composition such as the inkjetmethod. Also, when the RED 2 is 1.05 or less, separation between thepolymerizable compound and the porogen in the state of the liquidcomposition before the polymerization reaction starts is reduced so thatirregular or nonuniform porous resin is not easily formed.

Polymerization Initiator

The polymerization initiator can produce active species such as aradical or a cation upon application of energy such as light and heatand initiates polymerization of a polymerizable compound. It is suitableto use a known radical polymerization initiator, a cation polymerizationinitiator, a base producing agent, or a combination thereof. Of these,photoradical polymerization initiators are preferable.

Photoradical producing agents can be used as the photoradicalpolymerization initiator. For example, photoradical polymerizationinitiators such as Michler's ketone and benzophenone known by the tradename of Irgacure® and Darocur® are usable.

Specific examples include, but are not limited to, benzophenone andacetophenone derivatives such as α-hydroxy- or α-aminocetophenone,4-aroyl-1,3-dioxolane, benzyl ketal, 2,2-diethoxyacetophenone,p-dimethyl. aminoacetophene, p-dimethylamino propiophenone,benzophenone, 2-chlorobenzophenone, pp′-dichlorobenzophene,pp′-bisdiethylamino benzophenone, Michler's ketone, benzyl, benzoin,benzyldimethyl ketal, tetramethylthiuram monosulfide, thioxanthone,2-chlorothioxanthone, 2-methylthioxanthone, azobisisobutyronitrile,benzoin peroxide, di-tert-butyl peroxide, 1-hydroxy cyclohexyl phenylketone, 2-hydroxy-2-methyl-1-phenyl-1-one,1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, benzoin isopropyl ether, benzoin methyl ether, benzoin ethylether, benzoin ether, benzoin isobutyl ether, benzoin n-butyl ether, andbenzoin n-propyl, 1-hydroxy-cyclohexyl-phenyl-ketone,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl-ketone,2,2-dimethoxy-1,2-diphenylethane-1-one,bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium,bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,2-hydroxy-2-methyl-1-phenyl-propane-1-one (Darocur 1173),bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide,1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one-monoacylphosphineoxide, bisacylphosphine oxide or titanocene, fluorescene, anthraquinone,thioxanthone or xanthone, lophine dimer, trihalomethyl compound ordihalomethyl compound, active ester compound, and organoboron compound.

Furthermore, a photocrosslinking radical producing agent such as abisazide compound may be contained at the same time. When polymerizingonly with heat, a thermal polymerization initiator such asazobisisobutyronitrile (AIBN) which is a normal radical producing agentcan be used.

In order to obtain a sufficient curing speed, the proportion of thepolymerization initiator is preferably from 0.05 to 10.0 percent by massand more preferably from 0.5 to 5.0 percent by mass to the total mass(100.0 percent) of the polymerizable compound.

Method of Manufacturing Liquid Composition

It is preferable to manufacture the liquid composition by dissolving apolymerization initiator in a polymerization compound, furtherdissolving a porogen or other components in the polymerizable compound,and stirring the solution to obtain a uniform solution.

Properties of Liquid Composition

Viscosity of the liquid composition is preferably from 1.0 to 150.0mPa·s and more preferably from 1.0 to 30.0 mPa·s, and particularlypreferably from 1.0 to 25.0 mPa·s at 25 degrees C. in terms ofworkability when applying the liquid composition. When viscosity of theliquid composition is from 1.0 to 30.0 mPa·s, good dischargeability canbe maintained even when the liquid composition is applied to an inkjetmethod. Viscosity can be measured by, for example, a viscometer(RE-550L, manufactured by TOKI SANGYO CO., LTD.).

Device for Manufacturing Porous Resin and Method of Manufacturing PorousResin

FIG. 1 is a schematic diagram illustrating an example of the device formanufacturing a porous resin that executes the method of manufacturing aporous resin of the present embodiment.

Device for Manufacturing Porous Resin

A device 100 for manufacturing a porous resin manufactures a porousresin using the liquid composition mentioned above. The device 100 formanufacturing a porous resin includes a print processing unit 1 thatexecutes applying a liquid composition 7 onto a print substrate 4 toform a liquid composition layer thereon, a polymerization processingunit 2 that executes activating a polymerization initiator in the liquidcomposition layer to start polymerization of the polymerization compoundto obtain a porous resin precursor 6, and a heating unit 3 that executesheating the porous resin precursor 6 to obtain a porous resin. Thedevice 100 for manufacturing a porous resin further includes a conveyorunit 5 that conveys the print substrate 4. The conveyor unit 5 conveysthe print substrate 4 in the sequence of the print processing unit 1, apolymerization processing unit 2, and a heating unit 3 at a presetspeed.

Print Processing Unit

The printing process unit 10 includes a print device 1 a as an exampleof the application device that executes the application of the liquidcomposition 7 onto the print substrate 4, a storage container 1 b thatcontains the liquid composition 7, and a supply tube 1 c that suppliesthe liquid composition 7 stored in the storage container 1 b to theprint device 1 a.

The storage container 1 b accommodates the liquid composition 7. Theprint processing unit 1 discharges the liquid composition 7 from theprint device 1 a to apply the liquid composition 7 onto the printsubstrate 4 to form the liquid composition layer in a thin film likemanner. The storage container 1 b may be configured integrated with thedevice 100 for manufacturing a porous resin. Alternatively, it can beconfigured removable from the device 100 for manufacturing a porousresin. In addition, the storage container 1 b may be configured to addthe liquid composition 7 to the container 1 b integrated with the device100 for manufacturing a porous resin or the container 1 b detachablefrom the device 100 for manufacturing a porous resin.

The print device 1 a is not particularly limited as long as it can applythe liquid composition 7. For example, any printing device can be usedthat can execute the spin coating method, the casting method, the microgravure coating method, the gravure coating method, the bar coatingmethod, the roll coating method, the wire bar coating method, the dipcoating method, the slit coating method, the capillary coating method,the spray coating method, the nozzle coating method, the gravureprinting method, the screen printing method, the flexographic printingmethod, the offset printing method, the reverse printing method, theinkjet printing method, etc.

The storage container 1 b and the supply tube 1 c can be arbitrarilyselected as long as the liquid composition 7 can be stably stored andsupplied. The material constituting the storage container 1 b and thesupply tube 1 c preferably has a light shielding property in arelatively short wavelength range of ultraviolet and visible light. Dueto this light shielding property, the liquid composition 7 is preventedfrom starting being polymerized by external light.

Polymerization Processing Unit

As illustrated in FIG. 1 , the polymerization processing unit 2 includesa light irradiation device 2 a, which is an example of a curing devicethat executes a curing process for causing the liquid composition 7 tocure upon irradiation of active energy rays such as heat and light and apolymerization inert gas circulating device 2 b that circulates apolymerization inert gas. The light irradiation device 2 a irradiatesthe liquid composition layer formed by the printing processing unit 10with light in the presence of a polymerization inert gas to proceedphotopolymerization to obtain the porous resin precursor 6.

The light irradiation device 2 a is appropriately selected depending onthe absorption wavelength of the photopolymerization initiator containedin the liquid composition layer and is not particularly limited as longas it can start and proceed the polymerization of the compound in theliquid composition layer. For example, ultraviolet light sources such asa high-pressure mercury lamp, a metal halide lamp, a hot cathode tube, acold cathode tube, and an LED can be used. However, since light having ashorter wavelength generally tends to reach a deep part, it ispreferable to select a light source according to the thickness of theporous film to be formed.

Next, regarding the irradiation intensity of the light source of thelight irradiation device 2 a, if the irradiation intensity is toostrong, the polymerization proceeds rapidly before the phase separationsufficiently occurs, so that a porous structure tends to be difficult toobtain. In addition, when the irradiation intensity is too weak, thephase separation proceeds more than the microscale and the porousvariation and the coarsening are likely to occur. In addition, theirradiation time becomes longer and the productivity tends to decline.Therefore, the irradiation intensity is preferably 10 mW/cm² to 1 W/cm²and more preferably from 30 to 300 mW/cm².

Next, the polymerization inert gas circulation device 2 b plays a roleof reducing the polymerization active oxygen concentration contained inthe atmosphere and allowing the polymerization reaction of thepolymerizable compound near the surface of the liquid composition layerto proceed without inhibition. Therefore, the polymerization inert gasused is not particularly limited as long as it satisfies the functionmentioned above. For example, nitrogen, carbon dioxide, and argon can beused.

Moreover, regarding the flow rate, in terms of the inhibition reduction,O₂ concentration is preferably less than 20 percent (environment inwhich O₂ concentration is lower than atmosphere), more preferably from 0to 15 percent, and furthermore preferably from 0 to 5 percent. Further,it is preferable that the polymerization inert gas circulation device 2b include a temperature control device in order to stably proceedpolymerization.

Heating Unit

As illustrated in FIG. 1 , a heating unit 3 includes a heating device 3a and heats a solvent remaining in the porous resin precursor 6 formedby the polymerization processing unit 2 to dry and remove it. Thereby, aporous resin can be formed. The heating unit 3 may remove the solventunder a reduced pressure.

In addition, the heating unit 3 heats the porous film precursor 6 withthe heating device 3 a to promote the polymerization reaction in thepolymerization processing unit 2 and dry and remove thephotopolymerization initiator remaining in the porous film precursor 6.Note that it is not always necessary to promote the polymerization andremove the initiator simultaneously. The polymerization can be conductedbefore or after the solvent is removed.

Furthermore, the heating unit 330 heats the porous medium under areduced pressure to complete the polymerization after the solvent isremoved. The heating device 3 a is not particularly limited as long asit satisfies the function described above. Examples include, but are notlimited to, an IR heater and a hot air heater.

Further, the heating temperature and the time can be appropriatelyselected according to the boiling point of the solvent contained in theporous film precursor 6 and the formed film thickness.

Print Substrate

As the material of the print substrate 4, any material can be usedregardless of whether it is transparent or opaque. That is, as atransparent substrate, a glass substrate, a resin film substrate such asvarious plastic films, or a composite substrate thereof can be used. Asan opaque substrate, a silicon substrate, a metal substrate such asstainless steel, or a laminate of these substrates can be used.

The print substrate 4 includes, but are not limited to, a recordingmedium such as plain paper, gloss paper, special paper, and cloth.Further, the recording medium may be a low-permeable substrate(low-absorptive substrate). The low-permeable substrate has a surfacewith low moisture permeability, absorbency, and/or adsorption propertyand includes a material having myriad of hollow spaces inside but notopen to the exterior. Examples of the low-permeable substrate are coatedpaper for use in commercial printing and a recording medium like coatedpaper board having a middle layer and a back layer mixed with wastepaper pulp.

The print substrate 4 may be a porous resin sheet used as an insulatinglayer for a power storage element or a power generation element.

Moreover, the print substrate 4 having a curved surface or a rough formcan be used as long as it is applicable to the printing processing unit10 and the polymerization processing unit 2.

Porous Resin

The film thickness of the porous resin formed of the liquid compositionis not particularly limited. For example, in terms of curing uniformityduring polymerization, it is preferably from 0.01 to 500 μm, morepreferably from 0.01 to 100 μm, furthermore preferably from 1 to 50 μm,and particularly preferably from 10 to 20 μm. When the film thickness is0.01 μm or more, the surface area of the obtained porous resin isincreased and the function of the porous resin can be sufficientlydemonstrated. Moreover, when the film thickness is 500 μm or less,unevenness of light and heat used during polymerization in the filmthickness direction is reduced and a uniform porous resin can beobtained in the film thickness direction. This uniform porous resin inthe film thickness direction reduces structural unevenness of the porousresin and decreases deterioration of property of allowing liquid or gasto pass through. In addition, the film thickness of a porous resin issuitably adjusted according to the application of the porous resin. Forexample, when a porous resin is used as the insulating layer for a powerstorage element, it is preferably from 10 to 20 μm.

The formed porous resin is not particularly limited. For example, interms of securing good permeability of liquid and gas, the porous resinpreferably has a three-dimensional branched network structure of a curedresin as a skeleton and a co-continuous structure (also referred to as amonolith structure having multiple continuously connected pores. Thatis, it is preferable that the porous resin have a large number of poresand each pore thereof are communicated with ambient pores expanding inthree-dimensional directions. These pores communicating with each othersecure permeation of liquid and gas and helps to efficiently demonstratesubstance separation and reaction field.

One of the properties inherent to such a monolith structure is airpermeability. The air permeability of the porous resin is measuredaccording to, for example, JIS P8117 format and preferably 500seconds/100 mL or less and more preferably 300 seconds/100 mL or less.At the time, the air permeability is measured using, for example, aGurley type densometer (manufactured by TOYO SEIKI KOGYO CO. LTD.).

The cross-section of the pore of the formed porous resin may takevarious sizes and forms such as a substantially circular form, asubstantially elliptical form, and a substantially polygonal form. Thesize of the pore refers to the length of the longest portion in thecross-section. The size of the pore can be determined from across-section photograph taken by a scanning electron microscope (SEM).The size of the pores of the porous resin is not particularly limited.For example, it is preferably from 0.01 to 10 μm in terms ofpermeability of liquid and gas. The porosity of the porous resin ispreferably from 30 percent or more and more preferably 50 percent ormore. The method of controlling the size of the pore and the porosity ofthe porous resin within these ranges is not particularly limited.Examples include, but are not limited to, a method of controlling theproportion of the polymerizable compound in the liquid compositionwithin the range specified above, a method of controlling the proportionof the porogen in the liquid composition within the range specifiedabove, and a method of controlling the irradiation conditions of activeenergy rays.

Applications of Porous Resin

Application to Power Storage Element or Power Generation Element

The porous resin formed using the liquid composition of the presentembodiment can be used as, for example, an insulating layer for a powerstorage element or a power generation element. In other words, theliquid composition of the present embodiment can be used as a liquidcomposition for manufacturing an insulating layer for a power storageelement or a power generation element. For these applications, forexample, it is preferable to apply a liquid composition onto an activematerial layer formed on an electrode substrate in advance to form aninsulating layer (separator).

As the insulating layer for a power storage element or a powergeneration element, it is known to use, for example, a film-like porousinsulating layer having a predetermined size of pores or porosity. Whenthe liquid composition of the present embodiment is used, the proportionof the polymerizable compound, the proportion of the porogen, and theactive energy ray irradiation conditions, etc. can be appropriatelychanged to change the pore size and the porosity. Therefore, thelatitude of design is enhanced for the performance of the power storageelement and the power generation element. In addition, the liquidcomposition of the present embodiment can be applied by variousapplication methods. For example, it includes an ink jet method, so thatthe latitude of design can be enhanced for the forms of the powerstorage element and the power generation element.

In the insulating layer, the positive electrode and the negativeelectrode are separated and ion conductivity between the positiveelectrode and the negative electrode can be secured. In addition, theinsulating layer in the present application is not limited to alayer-like form.

In addition, when the liquid composition of the present embodiment canbe applied onto the insulating layer (first insulating layer) for thepower storage element or the power generation element, an insulatinglayer (second insulating layer) formed of a porous resin layer isadditionally formed. Due to the second insulating layer formed on thefirst insulating layer, heat resistance, impact resistance, and hightemperature shrinkage resistance, etc., as the whole insulating layercan be added or enhanced.

The electrode substrate is not particularly limited as long as it is aconductive substrate. For example, it includes a secondary battery and acapacitor, which are general power storage devices. Of these, aluminumfoil, copper foil, titanium foil, and etched foil in which fine holesare made by etching these, which can be suitably used for lithium ionsecondary batteries and perforated electrode substrates for use inlithium capacitors are suitable. Further, it is possible to use a wovenor non-woven flat carbon paper fibrous electrode used for a powergeneration device such as a fuel cell or a perforated electrodesubstrate having fine holes of the perforated electrode substratesmentioned above. Furthermore, in the case of a solar device, in additionto the electrode mentioned above, it is possible to use an article inwhich a transparent semiconductive thin film such as an indium titaniumbased oxide is formed on a flat glass or plastic substrate or an articleor an electroconductive electrode film such as zinc oxide is thinlyformed on a flat glass or plastic substrate or an article.

The active material layer is formed by dispersing a powdery activesubstance or catalyst composition in a liquid and applying the liquiddispersion onto an electrode substrate followed by fixing and drying.Normally, printing employing a spray, a dispenser, a die coater, orup-draw coating is used for the application, followed by drying.

The positive electrode active material is not particularly limited aslong as it is a material capable of reversibly intercalating anddeintercalating an alkali metal ion. Typically, an alkalimetal-containing transition metal compound can be used as the positiveelectrode active material. For example, the lithium-containingtransition metal compound includes a composite oxide containing lithiumand at least one element selected from the group consisting of cobalt,manganese, nickel, chromium, iron, and vanadium.

Specific examples include, but are not limited to, lithium-containingtransition metal oxides such as lithium cobaltate, lithium nickelate,and lithium manganate, an olivine type lithium salt such as LiFePO₄,chalcogen compounds such as titanium disulfide and molybdenum disulfide,and manganese dioxide. The lithium-containing transition metal oxide isa metal oxide containing lithium and a transition metal or a metal oxidein which the transition metal in the metal oxide is partiallysubstituted with a different element.

Specific examples of the different elements include, but are not limitedto, Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B. Ofthese, Mn, Al, Co, Ni and Mg are preferable. One or two or more kinds ofdifferent elements may be used. These positive electrode activematerials can be used alone or in combination. An example of the activematerial in the nickel metal hydride battery is nickel hydroxide.

The negative electrode active material is not particularly limited aslong as it is a material capable of reversibly intercalating anddeintercalating an alkali metal ion. Typically, a carbon materialcontaining graphite having a graphite-type crystal structure can be usedas the negative electrode active material. Examples of such a carbonmaterial include, but are not limited to, natural graphite, spherical orfibrous artificial graphite, non-graphitizable carbon (hard carbon), andgraphitizable carbon (soft carbon). An example of the material otherthan the carbon material is lithium titanate. To enhance the energydensity of the lithium ion battery, a high-capacity material such assilicon, tin, a silicon alloy, a tin alloy, silicon oxide, siliconnitride, or tin oxide can also be suitably used as the negativeelectrode active material.

Examples of the active material in the nickel metal hydride batteryinclude an AB2-based or A2B-based hydrogen intercalating alloy.

Specific examples of the binder for the positive electrode or negativeelectrode include, but are not limited to PVDF, PTFE, polyethylene,polypropylene, aramid resins, polyamide, polyimide, polyamideimide,polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester,polyacrylic acid ethyl ester, polyhexyl acrylate ester, polymethacrylicacid, polymethacrylic acid methyl ester, polymethacrylic acid ethylester, polymethacrylic acid hexyl ester, polyvinyl acetate,polyvinylpyrrolidone, polyether, polyethersulfone,hexafluoropolypropylene, styrene butadiene rubber, and carboxymethylcellulose. In addition, it is possible to use copolymers of two types ormore materials selected from the group consisting oftetrafluoroethylene, hexafluoroethylene, hexafluoropropylene,perfluoroalkyl vinyl ether, vinylidene fluoride,chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene,fluoromethyl vinyl ether, acrylic acid, and hexadiene. Two or moreselected from these may be mixed and used. Specific examples of theconductive agent contained in the electrode include, but are not limitedto, graphites such as natural graphite and artificial graphite, carbonblacks such as acetylene black, ketjen black, channel black, furnaceblack, lamp black, and thermal black, electroconductive carbon fiberssuch as carbon fiber and metal fiber, metal powders such as carbonfluoride and aluminum, electroconductive whiskers such as zinc oxide andpotassium titanate, electroconductive metal oxides such as titaniumoxide, electroconductive organic materials such as phenylene derivativesand graphene derivatives.

In general, for an active material in a fuel cell, as a catalyst for acathode electrode or an anode electrode, an article is used in whichmetal fine particles such as platinum, ruthenium, or a platinum alloyare borne on a catalyst bearer such as carbon. To carry the catalystparticle on the surface of the catalyst bearer, for example, thecatalyst bearer is suspended in water and the catalyst particleprecursor (which contains alloy components such as chloroplatinic acid,dinitrodiaminoplatinum, diplatinum chloride, platinum chloride,bisacetylacetate platinum, dichlorodiammine platinum, dichlorotetramineplatinum, diplatinum sulfate ruthenium acid, chloroiridate, rhodiumchloride, ferric chloride, cobalt chloride, chromium chloride, goldchloride, silver nitrate, rhodium nitrate, palladium chloride, nickelnitride, ion sulfate, and copper chloride) is added to the suspensionand dissolved therein. Thereafter, an alkali is added to produce ahydroxide of a metal and obtain a catalyst bearer on which the hydroxideis carried. The catalyst bearer is applied onto an electrode followed byreducing it under a hydrogen atmosphere, etc., thereby obtaining anelectrode onto which the catalyst particle (active material) is applied.

In the case of a solar cell, etc., the active material includes an oxidesemiconductor layer of SnO₂, ZnO, ZrO₂, Nb₂O₅, CeO₂, SiO₂, and Al₂O₃ inaddition to tungsten oxide powder and titanium oxide powder. In thesemiconductor layer, a dye is borne, which includes, but are not limitedto, a ruthenium-tris transition metal complex, a ruthenium-bistransition metal complex, an osmium-tris transition metal complex, anosmium-bis transition metal complex, a ruthenium-cis-diaqua-bipyridylcomplex, a phthalocyanine and porphyrin, and an organic-inorganicperovskite crystal.

Porogen and Electrolyte for Power Storage Element

When a porous resin formed by the liquid composition is used as aninsulation layer for a power storage element, the porogen is preferablyused as a component contained in an electrolytic solution constitutingthe power storage element. In other words, it is preferable that theelectrolytic solution contain a porogen and an electrolyte describedlater. A porogen suitably selected as a component contained in theelectrolyte as well as a component for forming a porous resin obviatesthe need for heating to remove the porogen after forming the porousresin and impregnating the porous resin with the electrolytic solution.

Due to the omission of heating, damage to the porous resin that can becaused by heating and damage to the components other than the porousresin (for example, an electrode substrate and an active material layer)can be reduced. In particular, due to reduction of damage to the porousresin, it is possible to prevent a short circuit in the power storageelement and diminish reaction unevenness while the power storage elementis driven, thereby further enhancing the performance of the powerstorage element.

Moreover, when removing the porogen by heating, the porogen maypartially remain in the porous medium. Such residual porogen may producegas due to unexpected side reaction inside the electric storage elementand degrade the performance of the power storage element. However, aporogen selected usable as the component contained in an electrolyte,for example, a material that does not easily degrade the performance ofthe power storage element due to a reaction, etc., can reduce thedeterioration of the performance.

When a porous resin is used as an insulating layer for a power storageelement, a porogen that diminishes decomposition reaction, gasproduction, etc. during charge and discharge of the power storageelement is preferably selected.

Specific examples include, but are not limited to, propylene carbonate,ethyl methyl carbonate, dimethyl carbonate, ethylene carbonate,acetonitrile, γ-butyrolactone, sulfolane, dioxolane, tetrahydrofuran,2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxy ethane,1,2-ethoxymethoxy ethane, polyethylene glycol, alcohols, and mixturesthereof. Of these, it is preferable to use at least one member selectedfrom the group consisting of propylene carbonate, ethyl methylcarbonate, dimethyl carbonate, and ethylene carbonate.

The boiling point of the porogen that does not require removing byheating after forming a porous resin is preferably higher than theboiling point of the porogen that requires removing by heating. When theboiling point is high, vaporization of porogen during production isdiminished and the composition of the electrolytic solution is preventedfrom changing from the originally assumed composition. The boiling pointis preferably 80 degrees C. or higher and more preferably 85 degrees C.or higher, and furthermore preferably 90 degrees C. or higher. Note thatthe boiling point of propylene carbonate is 240 degrees C., the boilingpoint of ethyl methyl carbonate is 107 degrees C., the boiling point ofdimethyl carbonate is 90 degrees C., and the boiling point of ethylenecarbonate is 244 degrees C.

As described above, when using a porogen functions as the component inan electrolyte constituting a power storage element, the device 100 formanufacturing a porous resin illustrated in FIG. 1 preferably does notinclude the heating unit 3.

As described above, the electrolyte is used when a porous resin formedof the liquid composition is used as an insulating layer for the powerstorage element. Examples of the electrolyte include a solid electrolytethat can be dissolved in a porogen and a liquid electrolyte such as anionic liquid. Due to the inclusion of the electrolyte in the liquidcomposition, the porogen and the electrolyte constituting the remainingcomponents can function as an electrolytic solution in the power storageelement after the porous resin is formed. This obviates the need forheating and removing the porogen and impregnating the porous resin withan electrolytic solution.

Due to the omission of heating, damage to the porous resin that can becaused by heating and damage to the components other than the porousresin (for example, an electrode substrate and an active material layer)can be reduced. In particular, due to reduction of damage to the porousresin, it is possible to prevent a short circuit in the power storageelement and diminish reaction unevenness while the power storage elementis driven, thereby further enhancing the performance of the powerstorage element.

Moreover, when removing the porogen by heating, the porogen maypartially remain in the porous medium. Such residual porogen may producegas due to unexpected side reaction inside the electric storage elementand degrade the performance of the power storage element. However, aporogen selected usable as the component contained in an electrolyte,for example, a material that does not easily degrade the performance ofthe power storage element due to a reaction, etc., can reduce thedeterioration of the performance.

The solid electrolyte is not particularly limited as long as it can bedissolved in porogen. Examples include inorganic ion salts such asalkali metal salts and alkali earth metal salts, quaternary ammoniumsalts, supporting salts of acids, and supporting salts of alkalis.Specific examples include, but are not limited to, LiClO₄, LiBF₄,LiAsF₆, LiPF₆, LiCF₃SO₃, LiCF₃COO, KCl, NaClO₃, NaCl, NaBF₄, NaSCN,KBF₄, Mg(ClO₄)₂, and Mg(BF₄)₂.

Examples of the liquid electrolyte include various ionic liquidscontaining a cation component and an anion component. It is preferablethat the ionic liquid can maintain a liquid state in a wide temperaturerange including room temperature.

Examples of the cationic component include, but are not limited to,imidazole derivatives such as N,N-dimethylimidazole salt,N,N-methylethylimidazole salt, N,N-methylpropylimidazole salt, aromaticsalts such as pyridinium derivatives such as N,N-dimethylpyridinium saltand N,N-methyl propylpyridinium salts, aliphatic quaternary ammoniumcompounds such as tetraalkylammonium such as trimethylpropyl ammoniumsalts, trimethylhexyl ammonium salts, and triethylhexyl ammonium salts.

As the anion component, for example, a compound containing fluorine ispreferable in terms of stability in the atmosphere. Specific examplesinclude, but are not limited to BF₄ ⁻, CF₃SO₃ ⁻, PF₄ ⁻, (CF₃SO₂)₂N⁻, andB(CN₄)⁻.

The proportion of the electrolyte in the electrolytic solution is notparticularly limited and can be suitably selected to suit to aparticular application. For example, it is preferably from 0.7 to 4.0mol/L, more preferably from 1.0 to 3.0 mol/L, and in terms of strikingbalance between the capacity and output of a power storage element,furthermore preferably from 1.0 to 2.5 mol/L.

Application to White Ink

Since the liquid composition of the present embodiment is whitened whenthe porogen is removed after forming a porous resin, for example, it ispreferable that the liquid composition be contained in white ink appliedto a recording medium. In the present application, the white ink is notparticularly limited as long as the ink is capable of forming a whiteimage. It includes a non-white substance in a form of ink, which is, forexample, transparent or colored other than white.

It is well known that a substance containing an inorganic pigment suchas titanium oxide as a coloring material exhibiting white. However,since such white ink has a large specific gravity and easilyprecipitates, the white ink involves problems with storage stability anddischarging stability. In that respect, the white ink of the presentembodiment can exhibit white even if it does not contain a whitecoloring material such as a pigment or dye as a component other than theliquid composition, so that the storage stability and the dischargingstability can be enhanced. The white ink of the present embodiment maycontain a white coloring material. However, containing substantially nowhite coloring material is preferable. Regarding containingsubstantially no white coloring material, it is preferable that theproportion of the white coloring material to the mass of white ink ispreferably 0.1 percent by mass or less, more preferably 0.05 percent bymass or less, furthermore preferably 0.01 percent by mass or less, andstill further preferably not greater than the detection limit.Particularly preferably, the white ink does not contain a white pigmentat all. When the white ink does not substantially contain a whitecoloring material, the white image formed by the white ink can bereduced in weight. For example, it can be suitably used as white ink foraircraft or vehicle painting.

Also, it is known that white ink containing a plurality of types ofpolymerizable compounds become cloudy due to phase separation of thesepolymers during curing. However, such a white ink exhibits white due tophase separation between the polymers but not due to the air layer, sothat it has a problem with the degree of whiteness. In this regard, whenthe liquid composition of the present embodiment is used as a white ink,the white color is exhibited by the porous resin having pores as the airlayer, so that a high level of whiteness can be exhibited. Note that thewhite means a color socially accepted as white. The degree of whitenesscan be evaluated by measuring lightness (L*) using a spectrophotometricdensitometer such as X-Rite 939, etc. For example, it is preferable thatthe lightness (L*) and chromaticity (a*, b*) be 70≤L*≤100, −4.5≤a*≤2,−6≤b*≤2.5 for 100 percent duty or more or when the surface of arecording medium is sufficiently covered.

Moreover, since the white ink of the present embodiment forms a layerformed of a porous resin when applied onto a recording medium, it can beused as primer ink with which an undercoat layer (primer layer) isformed to enhance fixability of other inks (for example, ink containinga coloring material) applied to the recording medium after the white inkis applied thereto.

In general, a low-permeable substrate such as coated paper, a glasssubstrate, a resin film substrate, or a low or non-permeable substratesuch as a metal substrate used as a recording medium has a problem withfixability of the ink to the substrate. In this regard, when the whiteink (primer ink) of the present embodiment is used, fixability of otherink applied onto an undercoat layer is enhanced because the white ink(primer ink) is well fixed onto a low or non-permeable substrate. Inaddition, if, a permeable ink (aqueous ink, etc.) that is difficult touse for a low-permeability substrate or a non-permeable substrate isused as the other ink (ink containing a coloring material, etc.) appliedlater, it is possible to fix the coloring material onto the surface ofthe porous resin while allowing the ink component to penetrate anddiffuse into the porous resin.

In addition, since the white ink (primer ink) forms a white receivinglayer, the color and transparency of the recording medium are concealedand the image density of the other ink (ink containing a coloringmaterial, etc.) applied later can be increased.

Application to Solid Freeform Fabrication

Since the liquid composition of this embodiment can form a porous resinlayer having a layer thickness in the height direction, athree-dimensional object can be formed by laminating multiple porousresin layers. That is, it is preferable that a composition for solidfreeform fabrication to fabricate a solid freeform fabrication objectcontain the liquid composition of this embodiment. In general, soldfreeform fabrication has a problem with distortion of a solid freeformfabrication object ascribable to curing shrinkage. In this respect,since the composition for solid freeform fabrication containing theliquid composition of this embodiment forms a porous medium having anetwork structure as a result of polymerization inducing phaseseparation, the internal stress during polymerization is relaxed due tothis network structure so that distortion of the solid freeformfabrication object caused by curing shrinkage can be reduced.

Next, a fabrication device and a fabrication method of fabricating asolid freeform fabrication object are described with reference to FIG. 2. FIG. 2 is a schematic diagram illustrating an example of thefabrication device employing a material jet method. The fabricationdevice illustrated in FIG. 2 includes a discharging device (an exampleof an applying unit) that discharges a liquid composition in an inkjetmethod, etc., and a curing unit that irradiates the discharged liquidcomposition with active energy rays to cure and repeats the dischargingby the discharging device and the curing by the curing device tofabricate a solid freeform fabrication object. In addition, thefabrication method executed by the fabrication device illustrated inFIG. 2 includes discharging a liquid composition according to an inkjetmethod and irradiating the discharged liquid composition with activeenergy rays to cure and repeats the discharging and the irradiatingsequentially to fabricate a solid freeform fabrication object.

This fabrication device and the fabrication method will be specificallydescribed. A fabrication device 39 illustrated in FIG. 2 forms laminatedlayers while discharging a first liquid composition for solid freeformfabrication from a discharging head unit 30 for solid freeformfabrication and a second liquid composition for solid freeformfabrication composed of different ingredients from the first liquidcomposition from discharging head units 31 and 32 for a support by usinga head unit having inkjet heads arranged movable in the directionsindicated by the arrows A and B and solidifying each of thesecompositions for solid freeform fabrication by ultraviolet irradiators33 and 34 placed adjacent to the discharging head units 31 and 32,respectively. More specifically, for example, after the discharging headunits 31 and 32 for a support discharge the second composition onto asubstrate 37 for supporting a fabrication object and irradiate thesecond liquid composition with active energy rays to cure to form afirst support layer having a hollow space (pool) for fabrication, thedischarging head unit 30 for fabrication object discharges the firstcomposition onto the hollow space followed by irradiation of activeenergy rays for solidification, thereby forming a first fabricationlayer. This step is repeated multiple times in accordance with therequired number of lamination while moving a stage 38 up and down in thevertical direction to laminate the support layer and the fabricationlayer to manufacture a solid freeform fabrication object 35. Thereafter,a laminated support 36 is removed, if desired. Although there is onlyone of the discharging head unit 30 for a fabrication object in FIG. 2 ,the device may have two or more discharging head units 30.

Application to Laminates

The liquid composition of the present embodiment can be applied tovarious objects such as a substrate and cure, whereby a porous resinlayer can be laminated on various objects such as the substrate. Inother words, it is preferable that the liquid composition of the presentembodiment be contained in a composition for a laminate to form alaminate including a target such as a substrate and a porous resin layerformed on the target. Examples include, as described above, liquidcompositions for use in a power storage element or a power generationelement, a liquid compositions for use in white ink, a liquidcomposition for use in a solid freeform fabrication. A liquidcomposition for use in the power storage element or the power generationelement is applied to the active material layer to laminate a porousresin layer as an insulating layer, a liquid composition for use inwhite ink is applied to a recording medium to form a porous resin layeras a white image, and a liquid composition for use in solid freeformfabrication is applied to the porous resin layer after curing tolaminate a porous resin layer as a predetermined layer of a solidfreeform fabrication object. In general, when a layer is laminated on atarget object such as a substrate, an interface exists between theobject and the layer. Therefore, when the adhesion at the interface isweak, the object and the layer are easily peeled off. In particular,when forming a layer and laminating the layers by polymerizationreaction, the polymer is likely to be distorted during polymerization,which tends to cause peeling-off between the object and the layer. Inthis regard, when the liquid composition of the present embodiment isused for a laminate, a porous medium having a network structure isformed along with polymerization-induced phase separation, so that theinternal stress during polymerization is relieved by the networkstructure. This is preferable because distortion of the fabricationobject ascribable to curing shrinkage is reduced and as a result,peeling-off of the object and the layer is prevented.

Application to Bearer

When the liquid composition of the present embodiment is mixed with afunctional substance to form a porous resin, a bearer having thefunctional substance borne on the surface of the porous resin can bemanufactured. In other words, the liquid composition of the presentembodiment and a composition containing a functional substance can beused as a composition for forming a bearer to manufacture a bearerbearing the functional material. The surface of the porous resin meansnot only the outer surface of the porous resin but also the innersurface communicating with the outside. Since the functional substancecan be borne in the void communicating with the outside, the surfacearea capable of bearing the functional substance is increased.

When the composition for forming a bearer of the present embodiment isused, the proportion of the polymerizable compound, the proportion ofthe porogen, and the active energy ray irradiation conditions, etc. canbe appropriately changed to change the pore size and the porosity.Therefore, the latitude of design is enhanced for the performance of thebearer. In addition, since the composition for forming a bearer of thepresent embodiment can be applied by various application methods, it canbe applied by, for example, an inkjet method, so that the latitude ofdesign can be enhanced for the forms of the bearer. Specifically, thebearer can be uniformly formed not only on a flat surface but also acurved surface, which obviates the need for cutting the bearer inaccordance with the form of the target to adjust the form. In addition,it is possible to form a bearer having a particle form by formingdroplets by discharging in an inkjet method and irradiating jetteddroplets in air or independent droplets attached onto a substrate withactive energy rays.

The functional substance directly or indirectly demonstrates apredetermined function and it is preferable that the function of thesubstance be enhanced or improved as the area of the substance borne ona porous resin increase. It is more preferable that the functionalsubstance borne on a porous resin demonstrate the function when locatedon the exterior surface and/or the interior surface communicating withthe outside (conversely, when the functional substance is located on theinternal surface not communicating with the outside, the function is notwell demonstrated). The functional substance may be dissolved ordispersed in a liquid composition. However, a dispersible functionalsubstance is preferable. Examples of the functional substance are notparticularly limited and include, but are not limited to, aphotocatalyst and a physiologically active substance.

Photocatalyst demonstrates photocatalytic active upon irradiation oflight (excitation light having an energy having a band gap or morebetween the valence band and conductive band of photocatalyst) in aparticular wavelength range. When photocatalyst is photocatalyticallyactive, it demonstrates various actions such as an antibacterial action,a deodorizing action, and a decomposing action of toxic substances suchas a volatile organic compound (VOC).

Specific examples of the photocatalyst include, but are not limited to,metal oxides such as anatase or rutyl type titanium oxide (IV) (TiO₂),tungsten oxide (III) (W₂O₃), tungsten oxide (IV) (WO₂), tungsten oxide(VI) (WO₃), zinc oxide (ZnO), iron oxide (III) (Fe₂O₃), strontiumtitanate (SrTiO₃), bismuth oxide (III) (Bi₂O₃), bismuth vanadate(BiVO₄), tin oxide (II) (SnO), tin oxide (IV) (SnO₂), tin oxide (VI)(SnO₃), zirconium oxide (ZrO₂), cerium (II) oxide (CeO), cerium (IV)oxide (CeO₂), barium titanate (BaTiO₃), indium (III) oxide (In₂O₃),copper (I) oxide (Cu₂O), copper oxide (II) (CuO), potassium tantalate(KTaO₃), and potassium niobate (KNbO₃), metal sulfides such as cadmiumsulfide (CdS), zinc sulfide (ZnS), and indium sulfide (InS), metalselenates such as cadmium selenate (CdSeO₄) and zinc selenide (ZnSe),metal nitrides such as gallium nitride (GaN). It is preferable tocontain at least one of titanium (IV) oxide (TiO₂), tin (IV) oxide(SnO₂), tungsten oxide (III) (W₂O₃), tungsten oxide (IV) (WO₂), andtungsten (VI) oxide (WO₃) and it is more preferable to contain anatasetype titanium (IV) oxide (TiO₂).

Physiologically active substances are an active ingredient used todemonstrate a physiological effect on a living body. Examples include,but are not limited to, polymers including biopolymers includingproteins such as antibodies and enzymes and nucleic acids such as DNAand RNA in addition to low molecular weight compounds includingpharmaceutical compounds, food compounds, and cosmetic compounds. Inaddition, according to the physiological effect, a physiologicallyactive substance demonstrates a physiological activity at a target site.For example, it causes quantitative and/or quality changes and impactson living bodies, tissues, cells, proteins, DNA, and RNA. In addition,physiological active means that a physiologically active substance actson a target site (for example, a target tissue) to cause changes orimpacts. The target site is preferably, for example, a receptor presenton or in the cell. In this case, a signal is transmitted to the cell dueto the physiological activeness of the physiologically active substancebinding to a specific receptor, resulting in demonstration of aphysiological effect. The physiologically active substance may beconverted into a mature form by an enzyme in a living body andthereafter binds with a specific receptor to demonstrate a physiologicaleffect. In this case, in the present disclosure, a substance beforebeing converted to a mature form is also included in the physiologicallyactive substance. The physiologically active substance may be created ina living organism (human or non-human organism) or may be artificiallysynthesized. When a particulate bearer is formed using a liquidcomposition containing such a physiologically active substance, thephysiologically active substance may be used as particles that deliverthe physiologically active substance to a target site in order todemonstrate a desired physiological effect, that is, particles for usein a drug delivery system (DDS) or sustained-release particles thatcontinue to release a drug over a long period of time. Further, when asheet-like bearer is formed using a liquid composition containing aphysiologically active substance, it can be used as a sustained-releasesheet that continuously releases a drug over a long period of time.

Application tor Surface Modification

The exterior surface of the porous resin formed by the liquidcomposition of the present embodiment has fine irregularities derivedfrom being porous so that wettability can be controlled. Specifically,when the resin constituting the porous resin is hydrophilic, a higherhydrophilicity can be imparted to the exterior surface of the porousresin than to a flat surface formed by the resin. In addition, when theresin constituting the porous resin is water repellent, a higher levelof water repellency can be imparted to the exterior surface of theporous resin than to the flat surface formed by the resin. Therefore,the surface modification layer can be formed by applying the surfacemodification liquid containing the liquid composition of the presentembodiment to the surface of a target object and the wettability of thesurface of the target object can be easily modified.

When the liquid composition of the present embodiment is used, theproportion of the polymerizable compound, the proportion of the porogen,and the active energy ray irradiation conditions, etc. can beappropriately changed to change the roughness (concave and convexascribable to pores and porosity) on the exterior surface of the porousresin. Therefore, the latitude of design is enhanced for the performanceof the surface modification layer. In addition, since the liquidcomposition of the present embodiment can be applied by variousapplication methods, it can be applied by, for example, an ink jetmethod, so that the latitude of design can be enhanced for the forms ofthe surface modification layer. Specifically, the surface modificationlayer can be uniformly formed not only on a flat surface but also on acurved surface.

Application to Separation Layer or Reaction Layer

When a fluid such as a liquid or a gas passes through the porous resinformed by the liquid composition of the present embodiment, the porousresin can be used as a fluid flow path. When the porous resin can beused as a fluid flow path, the porous resin can be used as a separationlayer for separating a predetermined substance from the fluid or as areaction layer (microreactor) that provides a minute reaction field tothe fluid. In other words, the liquid composition of the presentembodiment is preferably contained in the composition for forming aseparation layer or the composition for forming a reaction layer. It ispreferable that fluid can uniformly and efficiently pass through theporous resin for use in these applications. In this regard, the porousresin formed by the liquid composition of the present embodiment has aporous structure formed by phase separation. Therefore, the pores arecontinuously connected and the fluid uniformly and efficiently passesthrough the porous structure.

Fluid such as liquid and gas passing through the porous resin is notparticularly limited. For example, air permeability of the porous resinmeasured according to JIS P8117 format is preferably 500 seconds/100 mLor less and more preferably 300 seconds/100 mL or less. At the time, theair permeability is measured using, for example, a Gurley typedensometer (manufactured by TOYO SEIKI KOGYO CO. LTD.).

The separation means that a predetermined substance contained in a fluidmixture can be removed or concentrated. Regarding the removal, itincludes a case when a particular substance is partially or completelyremoved from a fluid mixture.

The reaction field refers to a place where a predetermined chemicalreaction proceeds when a predetermined substance contained in a fluidpasses through.

When used for a separation layer, the liquid composition of the presentembodiment preferably contains a polymerizable compound having afunctional group capable of interacting with a predetermined substancecontained in a fluid. When a porous resin is formed using the liquidcomposition, a functional group capable of interacting with apredetermined substance is arranged on the surface (inner surface andouter surface) of the porous resin, so that the predetermined substancecan be effectively separated. The polymerizable compound having afunctional group capable of interacting with a predetermined substancecontained in the fluid may be a part or all of the polymerizablecompound contained in the liquid composition. In the present disclosure,in addition to a case where the functional group itself can interactwith the predetermined substance, the functional group capable ofinteracting with a predetermined substance includes a case via anadditional graft polymerization.

When applied to a reaction layer, the liquid composition of the presentembodiment preferably contains a polymerizable compound having afunctional group providing a reaction field to a fluid. When a porousresin is formed using the liquid composition, a reaction field iseffectively provided because the functional group providing the reactionfield to a fluid is arranged on the surface (inner surface and outersurface) of the porous resin. The polymerizable compound having afunctional group providing a reaction field to a fluid may be a part orall of the polymerizable compound contained in the liquid composition.In the present disclosure, in addition to a case where the functionalgroup itself can provide a reaction field to a fluid, the functionalgroup providing a reaction field to a fluid includes a case where areaction field is provided via an additional graft polymerization.

The separation layer and the reaction layer can be formed by, forexample, filling a liquid composition in a container capable of forminga fluid inflow portion and a fluid outflow portion such as a glass tubeand causing it to cure. In addition, the separation layer and thereaction layer having a flow path with a desired shape formed of aporous resin can be produced (drawn) by printing the liquid compositionon a substrate by an inkjet method, etc. Since the flow paths of aseparation layer and a reaction layer can be printed, it is possible toprovide the separation layer and the reaction layer in which the flowpaths can be appropriately changed to suit to an application.

When the composition for forming a separation layer of the presentembodiment and the composition for forming a reaction layer of thepresent embodiment are used, the proportion of the polymerizablecompound, the proportion of the porogen, and the active energy rayirradiation conditions, etc. can be appropriately changed to change thepore size and the porosity of the porous resin. Therefore, the latitudeof design is enhanced for the performance of the separation layer andthe reaction layer.

Having generally described preferred embodiments of this disclosure,further understanding can be obtained by reference to certain specificexamples which are provided herein for the purpose of illustration onlyand are not intended to be limiting. In the descriptions in thefollowing examples, the numbers represent weight ratios in parts, unlessotherwise specified.

EXAMPLES

Next, the present disclosure is described in detail with reference toExamples but not limited thereto.

Calculation of Hansen Solubility Parameter C and Interaction Radius D ofPolymerizable Compound

According to the following procedure, Hansen solubility parameter C andthe interaction radius D was calculated for the following four types ofpolymerizable compounds.

-   -   Polymerizable compound X: Tricyclodecane dimethanol diacrylate        (manufactured by Daicel Ornex Co., Ltd.)    -   Polymerizable compound Y: ε-caprolactone-modified        tris-(2-acryloxyethyl)isocyanurate (manufactured by        Shin-Nakamura Chemical Co., Ltd.)    -   Polymerizable compound Z: pentaerythritol tetraacrylate        (manufactured by ARKEMA)    -   Polymerizable compound X+Y: a mixture of 50 percent by mass        polymerizable compound X and 50 percent by mass polymerizable        compound Y

Preparation of Composition for Measuring Transmission

First, a polymerizable compound whose Hansen solubility parameter C andthe interaction radius D were desired and the following 21 types ofsolvents for evaluation with known Hansen solubility parameters (HSP)were prepared and the polymerizable compound, each solvent forevaluation, and a polymerization initiator were mixed with the followingproportion to prepare a composition for measuring transmission.

Proportion of Composition for Measuring Transmission

-   -   Polymerizable compound whose Hansen solubility parameter C was        desired: 28.0 percent by mass    -   Solvent for evaluation with known Hansen solubility parameter        (HSP): 70.0 percent by mass    -   Polymerization initiator (Irgacure 819, manufactured by BASF        SE): 2.0 percent by mass

Solvent Group (21 types) for Evaluation

Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether,N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethylether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone,n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether,diethylene glycol butyl ether acetate, methyl ethyl ketone, methylisobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, and1-bromonaphthalene

Measurement of Light Transmission (Compatibility Evaluation)

The prepared composition for measuring transmission was infused into aquartz cell and the transmission of light (visible light) having awavelength of 550 nm of the composition for measuring transmission wasmeasured while stirring at 300 rpm using a stir bar. In this Example,when the light transmission was 30 percent or more, the polymerizablecompound and the solvent for evaluation were determined as compatible.When the light transmission was less than 30 percent, the polymerizablecompound and the solvent for evaluation were determined as incompatible.Various conditions regarding the measurement of light transmission areas follows:

-   -   Quartz cell: Special micro cell with screw cap (trade name:        M25-UV-2)    -   Transmission measuring device: USB4000, manufactured by Ocean        Optics, Inc    -   Rate of stirring: 300 rpm    -   Measuring wavelength: 550 nm    -   Reference: Light transmission measured at a wavelength of 550 nm        with the quartz cell filled with air (transmission: 100 percent)

The result of compatibility evaluation of the polymerizable compound andthe solvent for evaluation was shown in Table 1 according to thefollowing evaluation criteria.

Evaluation Criteria

a: Polymerizable compound and solvent for evaluation are compatible

b: Polymerizable compound and solvent for evaluation are not compatible

TABLE 1 Polymerizable compound Solvent for evaluation X Y Z X + YEthanol a b a a 2-Propanol a b a a Mesitylene a a a a Dipropylene glycolmonomethyl ether a a a a N-methyl2-pyrroridone a a a a γ-butyrolactone aa a a Propylene glycol monomethylether ether a a a a Propylene carbonatea a a a Ethyl acetate a a a a Tetrahydrofuran a a a a Acetone a a a an-tetradecane a b b b Ethylene glycol b b b b Diethylene glycolmonobutyl ether a a a a Diethylene glycol butyl ether acetate a a a aMethyl ethyl ketone a a a a Methyl isobutyl ketone a a a a2-ethylhexanol a b b a Diisobutyl ketone a a a a Benzyl alcohol a a a a1-Bromonaphtalene a a a a

Calculation by Hansen Solubility Sphere Method

Each of the Hansen solubility parameter (HSP) of the solvents forevaluation demonstrating compatibility and the Hansen solubilityparameter (HSP) of the solvents for evaluation not demonstratingcompatibility in the compatibility evaluation were plotted in the Hansenspace. Based on the Hansen solubility parameter (HSP) of each of theplotted solvents for evaluation, a virtual sphere (Hansen sphere) wascreated which included the Hansen solubility parameters (HSP) of thesolvent group for evaluation demonstrating compatibility and excludedthe Hansen solubility parameters of the solvent group for evaluation notdemonstrating compatibility. The center of the Hansen sphere wascalculated as the Hansen solubility parameter C and the radius of theHansen sphere was calculated as the interaction radius D.

Calculated Hansen Solubility Parameter C and Interaction Radius D

The calculated Hansen solubility parameter C and the interaction radiusD of the polymerizable compound were shown below.

-   -   Polymerizable compound X: Hansen solubility parameter C (17.21,        8.42, 7.98), interaction radius D (11.8)    -   Polymerizable compound Y: Hansen solubility parameter C (18.51,        9.04, 4.75), interaction radius D (9.5)    -   Polymerizable compound Z: Hansen solubility parameter C (19.65,        19.25, 4.48), interaction radius D (19.8)    -   Polymerizable compound X+Y: Hansen solubility parameter C        (17.71, 8.62, 8.67), interaction radius D (11.4)

Calculation of Hansen Solubility Parameter A and Interaction Radius B ofResin Formed by Polymerization of Polymerizable Compound

According to the following procedure, Hansen solubility parameter A andthe interaction radius B were calculated for the resin formed bypolymerizing the following four types of polymerizable compounds.

-   -   Polymerizable compound X: Tricyclodecane dimethanol diacrylate        (manufactured by Daicel Ornex Co., Ltd.)    -   Polymerizable compound Y: ε-caprolactone-modified tri        s-(2-acryloxyethyl)isocyanurate (manufactured by Shin-Nakamura        Chemical Co., Ltd.)    -   Polymerizable compound Z: pentaerythritol tetraacrylate        (manufactured by ARKEMA)    -   Polymerizable compound X+Y: a mixture of 50 percent by mass        polymerizable compound X and 50 percent by mass polymerizable        compound Y

Preparation of Composition for Measuring Haze

First, a precursor (polymerizable compound) of a resin whose Hansensolubility parameter A and the interaction radius B were desired and 21types of solvents for evaluation with known Hansen solubility parameters(HSP) were prepared and the polymerizable compound, each solvent forevaluation, and a polymerization initiator were mixed with the followingproportion to prepare a composition for measuring haze.

Proportion of Composition for Measuring Haze

-   -   Precursor (polymerizable compound) of resin whose Hansen        solubility parameter A was desired: 28.0 percent by mass    -   Solvent for evaluation with known Hansen solubility parameter        (HSP): 70.0 percent by mass    -   Polymerization initiator (Irgacure 819, manufactured by BASF        SE): 2.0 percent by mass

Solvent Group (21 types) for Evaluation

Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether,N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethylether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone,n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether,diethylene glycol butyl ether acetate, methyl ethyl ketone, methylisobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, and1-bromonaphthalene

Preparation of Element for Measuring Haze

Resin particulates were uniformly dispersed on an alkali-free glasssubstrate by spin coating to obtain a gap agent. Subsequently, thesubstrate coated with the gap agent and an alkali-free glass substrateto which no gap agent was applied were attached to each other in such amanner that the gap agent was sandwiched between the substrate and thealkali-free glass substrate. Next, the composition for measuring hazeprepared was filled into between the attached substrates utilizing thecapillary phenomenon to produce an element for measuring haze before UVirradiation. Subsequently, the element for measuring haze before UV wasirradiated with UV to cause the composition for measuring haze to cure.Finally, the periphery of the substrate was sealed with a sealant toprepare an element for measuring haze. Conditions at the time ofpreparation are as follows.

-   -   Alkali-free glass substrate: OA-10G, 40 mm, t=0.7 mm,        manufactured by Nippon Electric Glass Co., Ltd.    -   Gap agent: Resin fine particles Micropearl GS-L100, average        particle size 100 μm, manufactured by SEKISUI CHEMICAL CO., LTD.    -   Spin coating conditions: Amount of liquid dispersion 150 μL,        rate of rotation 1000 rpm, time of rotation 30 s    -   Amount of composition for measuring haze: 160 μL    -   UV irradiation conditions: UV-LED is used as a light source,        light source wavelength 365 nm, irradiation intensity 30 mW/cm²,        time of irradiation 20 seconds    -   Sealant: TB3035B (manufactured by ThreeBond Co., Ltd.)

Measurement of Haze Value (Cloudiness) (Compatibility Evaluation)

The haze value (cloudiness) was measured using the prepared element formeasuring haze before UV irradiation and the element for measuring haze.Using the measurement value for the element for measuring haze before UVirradiation as a reference (haze value 0), the increasing ratio of themeasurement value (haze value) for the element for measuring haze to themeasurement value (haze value) for the element for measuring haze beforeUV irradiation was calculated. In this Example, when the increase ratioof the haze value was 1.0 percent or more, the resin and the solvent forevaluation were determined as incompatible. When the increase ratio wasless than 1.0 percent, the resin and the solvent for evaluation weredetermined as compatible. The instruments used for the measurement areas follows.

-   -   Haze measuring device: Haze meter NDH5000, manufactured by        Nippon Denshoku Industries Co., Ltd.

The result of compatibility evaluation of the resin formed by thepolymerization of the polymerizable compound and the solvent forevaluation is shown in Table 2 according to the following evaluationcriteria.

Evaluation Criteria

a: Resin formed by polymerization of polymerizable compound and solventfor evaluation are not compatible

b: Resin formed by polymerization of polymerizable compound and solventfor evaluation are compatible

TABLE 2 Resin formed by polymerization of polymerizable compound (forconvenience, it is represented by the symbol of the polymerizablecompound used for the polymerization) Solvent for evaluation X Y Z X + YEthanol a a a a 2-Propanol a a a a Mesitylene b a a a Dipropylene glycolmonomethyl ether a a b a N-methyl2-pyrroridone b b b b γ-butyrolactone ab b b Propylene glycol monomethylether a a a a Propylene carbonate a b ba Ethyl acetate a a a a Tetrahydrofuran b b b b Acetone a a a an-tetradecane a a a a Ethylene glycol a a a a Diethylene glycolmonobutyl ether a a a a Diethylene glycol butyl ether acetate a a b aMethyl ethyl ketone a a a a Methyl isobutyl ketone a a a a2-Ethylhexanol a a a a Diisobutyl ketone a a a a Benzyl alcohol b b b b1-Bromonaphtalene b b b b

Calculation by Hansen Solubility Sphere Method

Each of the Hansen solubility parameter (HSP) of the solvents forevaluation demonstrating compatibility and the Hansen solubilityparameter (HSP) of the solvents for evaluation not demonstratingcompatibility in the measuring (compatibility evaluation) of haze value(cloudiness) were plotted in the Hansen space. Based on the Hansensolubility parameter (HSP) of each of the plotted solvents forevaluation, a virtual sphere (Hansen sphere) was created which includedthe Hansen solubility parameters (HSP) of the solvent group forevaluation demonstrating compatibility and excluded the Hansensolubility parameters of the solvent group for evaluation notdemonstrating compatibility. The center of the Hansen sphere wascalculated as the Hansen solubility parameter A and the radius of theHansen sphere was calculated as the interaction radius B.

Calculated Hansen solubility parameter A and Interaction radius B

Hansen solubility parameter A and the interaction radius B of the resinformed by polymerization of the calculated polymerizable compound are asfollows.

-   -   Resin formed by polymerization of polymerizable compound X:        Hansen solubility parameter A (20.02, 5.22, 6.15), interaction        radius B (8.3)    -   Resin formed by polymerization of polymerizable compound Y:        Hansen solubility parameter A (19.89, 10.47, 7.32), interaction        radius B (8.2)    -   Resin formed by polymerization of polymerizable compound Z:        Hansen solubility parameter A (21.59, 7.83, 7.75), interaction        radius B (11.4)    -   Resin formed by polymerization of polymerizable compound X+Y:        Hansen solubility parameter A (19.67, 9.68, 7.49), interaction        radius B (7.7)

Example 1-1

A liquid composition was prepared by mixing the materials in thefollowing proportions.

-   -   Polymerizable compound X: 28.0 percent by mass    -   Porogen (ethanol): 70.0 percent by mass    -   Polymerization initiator (Irgacure 819, manufactured by BASF        SE): 2.0 percent by mass

The relative energy difference (RED) calculated based on the followingrelationship 2 from the calculated Hansen solubility parameter C of thepolymerizable compound X, the calculated interaction radius D of thepolymerizable compound X, and Hansen solubility parameter of the solvent(porogen) was 0.998.Relative energy difference (RED) 2={Distance between (Hansen solutionparameter C of the polymerizable compound)+(Hansen solution parameter ofthe solvent)}/(interaction diameter D of the polymerizablecompound))  Relationship 2

Also, the relative energy difference (RED) calculated based on thefollowing relationship 1 from the calculated Hansen solubility parameterA of the resin formed by the polymerization of the polymerizablecompound X, the calculated interaction radius B of the resin formed bythe polymerization of the polymerizable compound X, and Hansensolubility parameter of the solvent (porogen) was 1.941.Relative energy difference (RED) 1={Distance between (Hansen solutionparameter A of the resin)+(Hansen solution parameter of thesolvent)}/(interaction diameter B of the resin)}   Relationship 1

Further, the viscosity of the liquid composition at 25 degrees C.measured using a viscometer (RE-550L, manufactured by TOKI SANGYO CO.,LTD.) was 30.0 mPa·s or less.

EXAMPLES AND COMPARATIVE EXAMPLES

The liquid composition of each Example and Comparative Example wasobtained in the same manner as in Example 1-1 except that thecomposition was changed to those shown in Tables 3 to 10. The values ofthe compositions shown in Tables 3 to 10 are represented in percent bymass. Also, the relative energy difference (RED) calculated based on therelationship 2 (represented as RED of polymerizable compound and porogenin Tables 3 to 10) and Relative energy difference (RED) calculated basedon the relationship 1 (Represented as RED of resin and porogen in Tables3 to 10) are show in Tables 3 to 10.

Also, viscosities at 25 degrees C. of the liquid compositions ofExamples and Comparative Examples are shown in Tables 3 to 10 accordingto the following evaluation criteria. In addition, in the evaluation oflight transmission described later, when the light transmission is lessthan 30 percent (evaluation b), in other words, when the components inthe liquid composition were determined as not compatible, the viscositythereof was not measured and—is shown in Tables 3 to 10.

Evaluation Criteria

a: Viscosity of the liquid composition is 30.0 mPa·s or less

b: Viscosity of the liquid composition is greater than 30.0 mPa·s

In Tables 3 to 10, EC/DMC/EMC mixture+LiPF₆ represents a solution inwhich LiPF₆ as an electrolyte was added to a mixture of ethylenecarbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate(EMC) (a mixture with a mass ratio of EC:DMC:EMC=2:2:1) in such a mannerthat the concentration of LiPF₆ was 1 mol/L. In Tables 3 to 10, forconvenience, solution containing LiPF₆ is shown in the column of solvent(porogen). In the present disclosure, the electrolyte such as LiPF₆ isnot defined as a component contained in the solvent (porogen) but acomponent that may be contained in the liquid composition.

TABLE 3 Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 Polymerizable X 28.028.0 28.0 28.0 28.0 28.0 28.0 28.0 compound Y Z X + Y Solvent Ethanol70.0 (porogen) 2-Propanol 70.0 Methyl decanoate 70.0 Ethylene glycol70.0 monobutyl ether Ethylene glycol 70.0 monoisopropyl ether Ethylmethyl carbonate 70.0 Dimethyl carbonate 70.0 Propylene carbonate 70.0EC/DMC/EMC mixture + LiPF₆ 1-Bromonaphtalene Tetrahydrofuran Benzylalcohol Cyclohexanone 1,3-butanediol Polymerization Irgacure 819 2.0 2.02.0 2.0 2.0 2.0 2.0 2.0 initiator RED of polymerizable compound 0.9980.778 0.576 0.505 0.481 0.270 0.325 0.995 and porogen RED of resin andporogen 1.941 1.603 1.010 1.220 1.330 1.125 1.230 1.559 Viscosity (mPa ·s) a a a a a a a a Example 1-9 1-10 1-11 1-12 1-13 1-14 1-15Polymerizable X 28.0 10.0 10.0 10.0 48.0 48.0 48.0 compound Y Z X + YSolvent Ethanol 89.5 50.0 (porogen) 2-Propanol 89.5 50.0 Methyldecanoate Ethylene glycol monobutyl ether Ethylene glycol 89.5 50.0monoisopropyl ether Ethyl methyl carbonate Dimethyl carbonate Propylenecarbonate EC/DMC/EMC mixture + 70.0 LiPF₆ 1-BromonaphtaleneTetrahydrofuran Benzyl alcohol Cyclohexanone 1,3-butanediolPolymerization Irgacure 819 2.0 0.5 0.5 0.5 2.0 2.0 2.0 initiator RED ofpolymerizable compound 0.427 0.998 0.778 0.481 0.998 0.778 0.481 andporogen RED of resin and porogen 1.356 1.941 1.603 1.330 1.941 1.6031.330 Viscosity (mPa · s) a a a a a a a

TABLE 4 Comparative Example 1-1 1-2 1-3 1-4 1-5 Polymerizable X 28.028.0 28.0 28.0 28.0 compound Y Z X + Y Solvent Ethanol (porogen)2-Propanol Methyl decanoate Ethylene glycol monobutyl ether Ethyleneglycol monoisopropyl ether Ethyl methyl carbonate Dimethyl carbonatePropylene carbonate EC/DMC/EMC mixture + LiPF₆ 1-Bromonaphtalene 70.0Tetrahydrofuran 70.0 Benzyl alcohol 70.0 Cyclohexanone 70.0 1:3-Butanediol 70.0 Polymerization Irgacure 819 2.0 2.0 2.0 2.0 2.0 initiator REDof polymerizable compound 0.800 0.241 0.555 0.263 1.102 and porogen REDof resin and porogen 0.382 0.809 0.999 0.670 2.000 Viscosity (mPa · s) aa a a —

TABLE 5 Example 2-1 2-2 2-3 2-4 2-5 Polymerizable X compound Y 28.0 28.028.0 28.0 28.0 Z X + Y Solvent Ethanol (porogen) 2-Propanol Methyldecanoate 70.0 Ethylene glycol 70.0 monobutyl ether Ethylene glycol 70.0monoisopropyl ether Ethyl methyl carbonate 70.0 Dimethyl carbonate 70.0Propylene carbonate EC/DMC/EMC mixture + LiPF₆ 1-BromonaphtaleneTetrahydrofuran Benzyl alcohol Cyclohexanone 1:3-Butane diolPolymerization Irgacure 819 2.0 2.0 2.0 2.0 2.0 initiator RED ofpolymerizable compound 0.804 1.040 1.029 0.636 0.820 and porogen RED ofresin and porogen 1.340 1.302 1.213 1.045 1.130 Viscosity (mPa · s) a aa a a Example 2-6 2-7 2-8 2-9 2-10 Polymerizable X compound Y 28.0 10.010.0 48.0 48.0 Z X + Y Solvent Ethanol (porogen) 2-Propanol Methyldecanoate Ethylene glycol 89.5 50.0 monobutyl ether Ethylene glycol 89.550.0 monoisopropyl ether Ethyl methyl carbonate Dimethyl carbonatePropylene carbonate EC/DMC/EMC mixture + 70.0 LiPF₆ 1-BromonaphtaleneTetrahydrofuran Benzyl alcohol Cyclohexanone 1:3-Butane diolPolymerization Irgacure 819 2.0 0.5 0.5 2.0 2.0 initiator RED ofpolymerizable compound 0.749 1.040 1.029 1.040 1.029 and porogen RED ofresin and porogen 1.051 1.302 1.213 1.302 1.213 Viscosity (mPa · s) a aa a a

TABLE 6 Comparative Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8Polymerizable X compound Y 28.0 28.0 28.0 28.0 28.0 28.0 28.0 28.0 Z X +Y Solvent Ethanol 70.0 (porogen) 2-Propanol 70.0 Methyl decanoateEthylene glycol monobutyl ether Ethylene glycol monoisopropyl etherEthyl methyl carbonate Dimethyl carbonate Propylene carbonate 70.0EC/DMC/EMC mixture + LiPF₆ 1-Bromonaphtalene 70.0 Tetrahydrofuran 70.0Benzyl alcohol 70.0 Cyclohexanone 70.0 1:3-Butane diol 70.0Polymerization Irgacure 819 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 initiatorRED of polymerizable compound 1.644 1.387 0.768 0.608 0.985 0.167 1.7540.997 and porogen RED of resin and porogen 1.790 1.582 0.996 0.955 0.9970.629 1.873 0.998 Viscosity (mPa · s) — — a a a a — a

TABLE 7 Example 3-1 3-2 3-3 3-4 3-5 3-6 Polymerizable X compound Y Z28.0 28.0 28.0 28.0 28.0 28.0 X + Y Solvent Ethanol 70.0 (porogen)2-Propanol 70.0 Methyl decanoate 70.0 Ethylene glycol 70.0 monobutylether Ethylene glycol 70.0 monoisopropyl ether Ethyl methyl carbonate70.0 Dimethyl carbonate Propylene carbonate EC/DMC/EMC mixture + LiPF₆1-Bromonaphtalene Tetrahydrofuran Benzyl alcohol Cyclohexanone1:3-Butane diol Polymerization Irgacure 819 2.0 2.0 2.0 2.0 2.0 2.0initiator RED of polymerizable compound 1.025 1.002 0.911 0.919 0.8190.748 and porogen RED of resin and porogen 1.443 1.277 1.095 1.085 1.0881.033 Viscosity (mPa · s) a a a a a a Example 3-7 3-8 3-9 3-10 3-11 3-12Polymerizable X compound Y Z 28.0 28.0 10.0 10.0 48.0 48.0 X + Y SolventEthanol 89.5 50.0 (porogen) 2-Propanol 89.5 50.0 Methyl decanoateEthylene glycol monobutyl ether Ethylene glycol monoisopropyl etherEthyl methyl carbonate Dimethyl carbonate 70.0 Propylene carbonateEC/DMC/EMC mixture + 70.0 LiPF₆ 1-Bromonaphtalene Tetrahydrofuran Benzylalcohol Cyclohexanone 1:3-Butane diol Polymerization Irgacure 819 2.02.0 0.5 0.5 2.0 2.0 initiator RED of polymerizable compound 0.796 0.6691.025 1.002 1.025 1.002 and porogen RED of resin and porogen 1.085 1.1121.443 1.277 1.443 1.277 Viscosity (mPa · s) a a a a a a

TABLE 8 Comparative Example 3-1 3-2 3-3 3-4 3-5 3-6 Polymerizable Xcompound Y Z 28.0 28.0 28.0 28.0 28.0 28.0 X + Y Solvent Ethanol(porogen) 2-Propanol Methyl decanoate Ethylene glycol monobutyl etherEthylene glycol monoisopropyl ether Ethyl methyl carbonate Dimethylcarbonate Propylene carbonate 70.0 EC/DMC/EMC mixture + LiPF₆1-Bromonaphtalene 70.0 Tetrahydrofuran 70.0 Benzyl alcohol 70.0Cyclohexanone 70.0 1:3-Butane diol 70.0 Polymerization Irgacure 819 2.02.0 2.0 2.0 2.0 2.0 initiator RED of polymerizable compound 0.843 0.7830.834 0.595 1.079 0.210 and porogen RED of resin and porogen 0.552 0.8610.777 0.706 1.459 0.988 Viscosity (mPa · s) a a a a — a

TABLE 9 Example 4-1 4-2 4-3 4-4 4-5 4-6 Polymerizable X compound Y Z X +Y 28.0 28.0 28.0 28.0 28.0 28.0 Solvent Ethanol 70.0 (porogen)2-Propanol 70.0 Methyl decanoate 70.0 Ethylene glycol 70.0 monobutylether Ethylene glycol 70.0 monoisopropyl ether Ethyl methyl carbonate70.0 Dimethyl carbonate Propylene carbonate EC/DMC/EMC mixture + LiPF₆1-Bromonaphtalene Tetrahydrofuran Benzyl alcohol Cyclohexanone1:3-Butane diol Polymerization Irgacure 819 2.0 2.0 2.0 2.0 2.0 2.0initiator RED of polymerizable compound 0.999 0.788 0.676 0.535 0.4920.405 and porogen RED of resin and porogen 1.854 1.609 1.331 1.292 1.2201.037 Viscosity (mPa · s) a a a a a a Example 4-7 4-8 4-9 4-10 4-11 4-12Polymerizable X compound Y Z X + Y 28.0 28.0 28.0 10.0 10.0 10.0 SolventEthanol 89.5 (porogen) 2-Propanol 89.5 Methyl decanoate Ethylene glycol89.5 monobutyl ether Ethylene glycol monoisopropyl ether Ethyl methylcarbonate Dimethyl carbonate 70.0 Propylene carbonate 70.0 EC/DMC/EMCmixture + 70.0 LiPF₆ 1-Bromonaphtalene Tetrahydrofuran Benzyl alcoholCyclohexanone 1:3-Butane diol Polymerization Irgacure 819 2.0 2.0 2.00.5 0.5 0.5 initiator RED of polymerizable compound 0.393 0.393 0.4990.999 0.788 0.535 and porogen RED of resin and porogen 1.132 1.132 1.0861.854 1.609 1.292 Viscosity (mPa · s) a a a a a a Example 4-13 4-14 4-154-16 4-17 Polymerizable X compound Y Z X + Y 10.0 48.0 48.0 48.0 48.0Solvent Ethanol 50.0 (porogen) 2-Propanol 50.0 Methyl decanoate Ethyleneglycol 50.0 monobutyl ether Ethylene glycol 89.5 50.0 monoisopropylether Ethyl methyl carbonate Dimethyl carbonate Propylene carbonateEC/DMC/EMC mixture + LiPF₆ 1-Bromonaphtalene Tetrahydrofuran Benzylalcohol Cyclohexanone 1:3-Butane diol Polymerization Irgacure 819 0.52.0 2.0 2.0 2.0 initiator RED of polymerizable compound 0.492 0.9990.788 0.535 0.492 and porogen RED of resin and porogen 1.220 1.854 1.6091.292 1.220 Viscosity (mPa · s) a a a a a

TABLE 10 Comparative Example 4-1 4-2 4-3 4-4 4-5 Polymerizable Xcompound Y Z X + Y 28.0 28.0 28.0 28.0 28.0 Solvent Ethanol (porogen)2-Propanol Methyl decanoate Ethylene glycol monobutyl ether Ethyleneglycol monoisopropyl ether Ethyl methyl carbonate Dimethyl carbonatePropylene carbonate EC/DMC/EMC mixture + LiPF₆ 1-Bromonaphtalene 70.0Tetrahydrofuran 70.0 Benzyl alcohol 70.0 Cyclohexanone 70.0 1:3-Butanediol 70.0 Polymerization Irgacure 819 2.0 2.0 2.0 2.0 2.0 initiator REDof polymerizable compound 0.808 0.307 0.501 0.314 1.095 and porogen REDof resin and porogen 0.996 0.915 0.985 0.599 1.944 Viscosity (mPa · s) aa a a —

Next, light transmission of the liquid composition, haze change rate,pore diameter measurement, resin porosity, and discharging stabilitywere evaluated.

Light Transmission

The liquid composition of each of Examples and Comparative Examples wereused to measure the light transmission according to the followingprocedure.

The prepared liquid composition was infused into a quartz cell and thetransmission of light (visible light) having a wavelength of 550 nm ofthe liquid composition was measured while being stirred at 300 rpm usinga stir bar. In this Example, when the light transmission was 30 percentor more, the polymerizable compound and the porogen were determined ascompatible. When the light transmission was less than 30 percent, thepolymerizable compound and the porogen were determined as incompatible.Various conditions regarding the measurement of light transmission areas follows:

-   -   Quartz cell: Special micro cell with screw cap (trade name:        M25-UV-2)    -   Transmission measuring device: USB4000, manufactured by Ocean        Optics, Inc    -   Rate of stirring: 300 rpm    -   Measuring wavelength: 550 nm    -   Reference: Light transmission measured at a wavelength of 550 nm        with the quartz cell filled with air (transmission: 100 percent)

The results of light transmission are shown in Tables 11 to 14 accordingto the following evaluation criteria.

Evaluation Criteria

a: Light transmission is 30 percent or more

b: Light transmittance is less than 30 percent

Haze Change Rate

Using the adjusted liquid compositions of Examples and ComparativeExamples, the haze value (cloudiness) of the element for measuring hazewas measured according to the following procedure.

Preparation of Element for Measuring Haze

Resin particulates were uniformly dispersed on an alkali-free glasssubstrate by spin coating to obtain a gap agent. Subsequently, thesubstrate coated with the gap agent and an alkali-free glass substrateto which no gap agent was applied were attached to each other in such amanner that the gap agent was sandwiched between the substrate and thealkali-free glass substrate. Next, the prepared liquid composition wasfilled into between the attached substrates utilizing the capillaryphenomenon to produce an element for measuring haze before UVirradiation. Subsequently, the element for measuring haze before UV wasirradiated with UV to cause the composition for measuring haze to cure.Finally, the periphery of the substrate was sealed with a sealant toprepare an element for measuring haze. Various conditions at the time ofpreparation are as follows.

-   -   Alkali-free glass substrate: OA-10G, 40 mm, t=0.7 mm,        manufactured by Nippon Electric Glass Co., Ltd.    -   Gap agent: Resin fine particles Micropearl GS-L100, average        particle size 100 μm, manufactured by SEKISUI CHEMICAL CO., LTD.    -   Spin coating conditions: Amount of liquid dispersion 150 μL,        rate of rotation 1000 rpm, time of rotation 30 s    -   Filled liquid composition: 160 μL    -   UV irradiation conditions: UV-LED is used as a light source,        light source wavelength 365 nm, irradiation intensity 30 mW/cm²,        time of irradiation 20 seconds    -   Sealant: TB3035B (manufactured by ThreeBond Co., Ltd.)

Measurement of Haze Value (Cloudiness)

The haze value (cloudiness) was measured using the prepared element formeasuring haze before UV irradiation and the element for measuring haze.Using the measurement value for the element for measuring haze before UVirradiation as a reference (haze value 0), the increasing ratio of themeasurement value (haze value) for the element for measuring haze to themeasurement value (haze value) for the element for measuring haze beforeUV irradiation was calculated. In this Example, when the increase ratioof the haze value was 1.0 percent or more, the resin and the porogenwere determined as incompatible. When the increase ratio was less than1.0 percent, the resin and the porogen were determined as compatible.The instruments used for the measurement are as follows.

-   -   Haze measuring device: Haze meter NDH5000, manufactured by        Nippon Denshoku Industries Co., Ltd.

The results of the increasing ratio of haze value are shown in Tables 11to 14 according to the following evaluation criteria. Note that in theevaluation of the light transmission described above, when the componentof the liquid composition was determined as incompatible, the liquidcomposition was not subject to an evaluation and—was shown in Tables 11to 14.

Evaluation Criteria

a: Increase ratio of haze value is 1.0 percent or more

b: Increase ratio of haze value is less than 1.0 percent

Measurement of Pore Diameter

After applying 20 μl of the liquid composition of each Example andComparative Example onto copper foil with a thickness of 8 μm as asubstrate using a dispenser (micro-determination dispenser NANO MASTERSMP-II, manufactured by Musashi Engineering, Inc.), a polymerizablecompound was polymerized by irradiating with UV in an N₂ atmosphere.Next, using a hot plate, the solvent was removed by heating at 100degrees C. for one minute to form a resin. The UV irradiation conditionsare as follows:

-   -   Light source: UV-LED (FJ800, manufactured by Phoseon Technology)    -   Wavelength of light source: 365 nm    -   Irradiation intensity: 30 mW/cm²    -   Irradiation time: 20 seconds    -   Device for measuring amount of UV irradiation: UV integrated        light meter UIT-250, manufactured by Ushio Inc.

Next, the surface of the produced resin was observed with an SEM. As aresult, in the evaluation of the light transmission described above, allthe liquid compositions were confirmed to form resins having a pore sizeof from 0.01 to 10 μm excluding the liquid compositions containingcomponents determined as not compatible (evaluated as b for lighttransmission in Tables 11 to 14). The formed resin having pores had aco-continuous structure in which a plurality of pores in the resin werecontinuously connected. In addition, in the evaluation of the lighttransmission described above, the liquid compositions containingcomponents determined as not compatible (evaluated as b for theevaluation of light transmission in Tables 11 to 14) did not form aresin having a pore of from 0.01 to 10

Porosity of Resin

In the same manner as the evaluation of the measuring of the porediameter mentioned above, resins were formed using the liquidcompositions of each Example and Comparative Example.

Next, after filling the produced resin with an unsaturated aliphaticacid (commercially available butter) and osmium staining, the internalcross-section structure was cut out with FIB and the porosity in theresin was measured using an SEM. The results of porosity of the resinare shown in Tables 11 to 14 according to the following evaluationcriteria. Note that the produced resins which were not porous resinswere not subject to the evaluation and—was shown in Tables 11 to 14.

Evaluation Criteria

a: Porosity is 50 percent or more

b: Porosity is from 30 to less than 50 percent

c: Porosity is less than 30 percent

Discharging Stability

The liquid composition of each Example and Comparative Example wascontinuously discharged for 60 minutes using an inkjet dischargingdevice equipped with a GENS head (manufactured by Ricoh Printing SystemsCo., Ltd.), the number of nozzles of nozzle omission was counted, anddischarging stability was not evaluated based on the followingevaluation criteria. For the inkjet discharging device, the drivefrequency and the heating temperature were appropriately adjusted foreach ink and the discharging amount of ink per discharging was set to 2pL. Nozzle omission means clogged nozzles that cannot discharge inkdroplets. The results of discharging stability are shown in Tables 11 to14 according to the following evaluation criteria. Note that in theevaluation of the light transmission described above, when the componentof the liquid composition was determined as incompatible, the liquidcomposition was not subject to an evaluation and “-” was shown in Tables11 to 14.

Evaluation Criteria

a: Number of nozzles of nozzle omission is less than 5

b: Number of nozzles of nozzle omission is not less than 5 althoughdischargeable nozzles are present

c: All nozzles are not dischargeable

TABLE 11 Light Haze Porosity Discharging transmission change ratio ofresin stability Example 1-1 a a a a Example 1-2 a a a a Example 1-3 a ab a Example 1-4 a a b a Example 1-5 a a a a Example 1-6 a a a a Example1-7 a a a a Example 1-8 a a a a Example 1-9 a a a a Example 1-10 a a a aExample 1-11 a a a a Example 1-12 a a a a Example 1-13 a a a a Example1-14 a a a a Example 1-15 a a b a Comparative a b c a Example 1-1Comparative a b c a Example 1-2 Comparative a b c a Example 1-3Comparative a b c a Example 1-4 Comparative b — — — Example 1-5

TABLE 12 Light Haze Porosity Discharging Transmission change ratio ofResin stability Example 2-1 a a a a Example 2-2 a a a a Example 2-3 a aa a Example 2-4 a a b a Example 2-5 a a b a Example 2-6 a a a a Example2-7 a a b a Example 2-8 a a a a Example 2-9 a a b a Example 2-10 a a b aComparative b — — — Example 2-1 Comparative b — — — Example 2-2Comparative a b c a Example 2-3 Comparative a b c a Example 2-4Comparative a b c a Example 2-5 Comparative a b c a Example 2-6Comparative b — — — Example 2-7 Comparative a b c a Example 2-8

TABLE 13 Light Haze Porosity Discharging Transmission change ratio ofResin stability Example 3-1 a a a a Example 3-2 a a a a Example 3-3 a aa a Example 3-4 a a b a Example 3-5 a a b a Example 3-6 a a b a Example3-7 a a b a Example 3-8 a a a a Example 3-9 a a a a Example 3-10 a a b aExample 3-11 a a a a Example 3-12 a a a a Comparative a b c a Example3-1 Comparative a b c a Example 3-2 Comparative a b c a Example 3-3Comparative a b c a Example 3-4 Comparative b — — — Example 3-5Comparative a b c a Example 3-6

TABLE 14 Light Haze Porosity Discharging Transmission change ratio ofResin stability Example 4-1 a a a a Example 4-2 a a a a Example 4-3 a aa a Example 4-4 a a a a Example 4-5 a a a a Example 4-6 a a b a Example4-7 a a b a Example 4-8 a a b a Example 4-9 a a b a Example 4-10 a a a aExample 4-11 a a a a Example 4-12 a a a a Example 4-13 a a a a Example4-14 a a a a Example 4-15 a a a a Example 4-16 a a b a Example 4-17 a ab a Comparative a b c a Example 4-1 Comparative a b c a Example 4-2Comparative a b c a Example 4-3 Comparative a b c a Example 4-4Comparative b — — — Example 4-5

As seen in the results shown in Tables 11 to 14, when the relativeenergy difference (RED) 2 calculated based on the relationship 2 abovefrom the Hansen solubility parameter C of the polymerizable compound,the interaction radius D of the polymerizable compound, and the Hansensolubility parameter of the solvent (porogen) is 1.05 or less, itindicates that the polymerizable compound and the solvent (porogen) arehighly compatible. In addition, when the relative energy difference(RED) 1 calculated based on the relationship 1 above from the Hansensolubility parameter A of the resin formed by polymerization of thepolymerizable compound, the interaction radius B of the resin, and theHansen solubility parameter of the solvent (porogen) was 1.00 orgreater, it means that compatibility between the resin formed by thepolymerization of a polymerizable compound and the solvent (porogen) islow.

This means that, due to the selection of a suitable combination of apolymerizable compound and a solvent (porogen), the polymerizablecompound and the solvent (porogen) changes from a compatible state to anincompatible state in accordance with the polymerization reactionderived from UV irradiation, which causes phase separation, therebyforming a porous resin. Specifically, upon UV irradiation, thepolymerizable compound is polymerized, gradually forming a resin. Duringthis process, solubility of the growing resin in the solvent (porogen)decreases, which causes phase separation. As a result, the resin isseparated from the solution and finally forms a network structure havinga porous structure with pores filled with the solvent (porogen). This isconsidered to increase the haze value. Moreover, the porogen is removedby drying the network structure, thereby obtaining a porous resin havinga high porosity.

In addition, this was true not only in the case in which one typepolymerizable compound was used but also the case in which two or moretypes of polymerizable compounds were mixed.

In the present embodiment, although a dispersion composition containinga dispersion in a liquid composition is suitable, a non-dispersioncomposition containing no dispersion in a liquid composition ispreferable as in Examples. If the liquid composition is a non-dispersioncomposition, the liquid composition can be used in an application devicethat applies various types of liquid compositions. For example, it ispreferable because it can be stably used in an inkjet method which isrequired to maintain discharging stability.

Moreover, all the porous resins formed using the liquid composition ofExamples were white and confirmed to be usable as white ink.Furthermore, discharging stability of the liquid compositions ofExamples were excellent when the liquid compositions were discharged byan inkjet discharging device. The liquid compositions were confirmed tobe suitably usable as white ink discharged in the inkjet method.

Numerous additional modifications and variations are possible in lightof the above teachings. It is therefore to be understood that, withinthe scope of the above teachings, the present disclosure may bepracticed otherwise than as specifically described herein. With someembodiments having thus been described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the scope of the present disclosure and appended claims,and all such modifications are intended to be included within the scopeof the present disclosure and appended claims.

What is claimed is:
 1. A method of manufacturing a porous resin, themethod comprising: discharging a liquid composition that can form theporous resin having a pore size of from 0.01 to 10 μm, to obtain adischarged liquid composition; and curing the discharged liquidcomposition, wherein the liquid composition comprises a polymerizablecompound and a solvent which is a porogen, wherein the liquidcomposition has a viscosity of from 1 to 30 mPa·s at 25 degrees C., andwherein the liquid composition contains a liquid that is not a porogenin a proportion of from 0 to 10.0 percent by mass of the total amount ofthe liquid composition.
 2. The method of claim 1, wherein the liquidcomposition comprises: from 10.0 to 50.0 percent by mass of thepolymerizable compound, and from 50.0 to 90.0 percent by mass of thesolvent.
 3. The method of claim 1, wherein the liquid composition has aviscosity of from 1 to 25 mPa·s at 25 degrees C.
 4. The method of claim1, wherein the polymerizable compound comprises a (meth)acryloyl groupor a vinyl group.
 5. The method of claim 1, wherein the porous resin hasa porosity of 30 percent or higher.
 6. The method of claim 1, whereinthe porous resin is a monolith comprising multiple continuouslyconnected pores.
 7. The method of claim 1, wherein the liquidcomposition further comprises an electrolyte.
 8. A The method of claim1, wherein the solvent comprises at least one compound selected from thegroup consisting of polypropylene carbonate, ethylmethyl carbonate,dimethyl carbonate, and ethylene carbonate.
 9. The method of claim 1,wherein the liquid composition when stirred transmits at least 30percent of incident light having a wavelength of 550 nm.
 10. The methodof claim 1, wherein the liquid composition comprises: from 20.0 to 40.0percent by mass of the polymerizable compound, and from 60.0 to 80.0percent by mass of the solvent.
 11. The method of claim 2, wherein thepolymerizable compound comprises a (meth)acryloyl group.
 12. The methodof claim 2, wherein the polymerizable compound comprises a vinyl group.13. The method of claim 2, wherein the solvent comprises at least onecompound selected from the group consisting of polypropylene carbonate,ethylmethyl carbonate, dimethyl carbonate, and ethylene carbonate. 14.The method of claim 4, wherein the solvent comprises at least onecompound selected from the group consisting of polypropylene carbonate,ethylmethyl carbonate, dimethyl carbonate, and ethylene carbonate. 15.The method of claim 5, wherein the solvent comprises at least onecompound selected from the group consisting of polypropylene carbonate,ethylmethyl carbonate, dimethyl carbonate, and ethylene carbonate. 16.The method according to claim 1, wherein when an element comprising theliquid composition is cured, a haze value of the element increased by1.0 percent or more.
 17. The method according to claim 1, wherein thepolymerizable compound is tricyclodecane dimethanol diacrylate.
 18. Themethod according to claim 1, wherein the polymerizable compound isε-caprolactone-modified tri-(2-acryloxyethyl)isocyanurate.
 19. Themethod according to claim 1, wherein the polymerizable compound ispentaerythritol tetraacrylate.
 20. The method according to claim 1,wherein the liquid composition contains the liquid that is not a porogenin a proportion of from 0 to 5.0 percent by mass of the total amount ofthe liquid composition.
 21. The method according to claim 1, wherein theliquid composition contains the liquid that is not a porogen in aproportion of from 0 to 1.0 percent by mass of the total amount of theliquid composition.